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BLOCK – I
1
UNIT-1 STEREO CHEMISTRY IN MAIN GROUP COMPOUNDS
Structure:
1.0 Introduction
1.1 Objectives
1.2 Valence Shell Electron Pair Repulsion (VSEPR)
1.2.1 Gillespie Laws
1.2.2 Applications
1.2.3 Comparison of CH4, NH3, H2O and H3O+
1.2.4 Comparison of PF5, SF4 and [ICl2-]
1.3 Walsh Diagrams
1.3.1 Application to triatomic molecules.
1.3.2 Application to penta atomic molecules.
1.4 d - p Bonds.
1.4.1 Phosphorous Group Elements.
1.4.2 Oxygen Group Elements.
1.5 Bent's rule and Energetic of hybridisation.
1.5.1 III and IV groups halides.
1.5.2 V and VI groups Hydrides halides.
1.5.3 Isovalent hybridisation.
1.5.4 Apicophilicity.
1.6 Some simple reactions of covalently bonded molecules.
1.6.1 Atomic invevsion.
1.6.2 Berrypseudo rotation.
1.6.3 Nucleophillic substitution.
1.7 Let Us Sum Up.
1.8 Check Your Progress: The key.
2
1.0 INTRODUCTION
You may recall what you have already studied about the directional
property of a covalent bond and the concept of hybridisation of orbital to
predict molecular geometry.
1.1 OBJECTIVES
3
1.2 VSEPR THEORY (VALENCE SHELL ELECTRON PAIR
REPULSION THEORY)
In other words we can say that the shape of covalent molecule will
be linear for 2 bonding electron pairs, triangular for 3 bonding
electron pairs. tetrahedral for 4 bonding electron pairs, trigonal
bipyramidal for 5 bonding electron pairs:
Name of Bonding Shape
Compound Electron Pairs
BeCl2 2 Linear
BeCl3 3 Triangular Planar
SnCl4 4 Regular Tetrahedral
PCl5 5 Trigonal bipyramidal
SF6 6 Regular Octahedral
4
2. When the central atom in a molecule is surrounded by both,
bonding electron pairs as well as by lone pairs, then molecule will
not have a regular shape. The geometry of the molecule will be
disturbed. This alteration or distortion in shape is due to the
alteration in bond angles which arises due to the presence of lone
pairs on the central atom. How the presence of lone pairs causes an
alteration in bond angles can be explained as follows:
5
The more the numbers of lone pairs on a central metal atom,
the greater is the contraction caused in the angle between the
bonding pairs. This fact is clear when we compare the bond angles
in CH4, NH3 and H2O molecules. (Table 1.1)
Table 1.1
Molecules No. of Lone Bond Contraction in
pairs on Angle bond angle
central atom w.r.t. CH4
CH4 0 109.5o 0
NH3 1 107.5o 2o
H2O 2 105.5o 4o
5. Repulsion between electron pairs in filled shells are larger than the
repulsion between electron pairs in incompletely filled shells.
Examples: H2O (105.5o) < H2S (92.2o)
6
(b) If the molecule is AX3 (I) or AX2 with a lone pair of
electrons on the central atom A, i.e. AX2E (II), then the
molecule will be triangular (Fig 1.1):
(VI) (IX)
7
(VIII) (IX)
8
characteristic bond angle of 109.5o. NH3 is pyramidal (Three bond pairs
and one lone pair) and has a bond angle of 107o. While H2O is angular
(Two bond-pairs and two lone-pairs) and has bond angle of 105o. The
increasing lp-lp repulsion decreases the bond angles from 109.5o to
~107o in NH3 and ~105.5o in H2O. On comparing H3O+ with these
molecules, we notice that, it resembles with NH3 molecule. As the central
atom of H3O+ on (Oxygen) is also sp3 hybridised and has 3bp+1 lp. Thus
H3O+ will also be pyramidal with a bond angle of ~107o. (Fig 1.5)
9
SF4 molecule has 4 bond-pairs and one lone pair on the central S
atom. The lp in this molecule has two options- it can sit in a axial or in an
equatorial orbital. In the axial position (Fig. 1.6 (b))i)) it has three bps at
90o and one bp directly opposite to itself. While in equatorial position
(Fig. 1.6 (b)(ii)) it has two bps at 90o and two bps at 120o. As in the
equatorial position lp-bp repulsion is less and expansion is easy the lp
prefers the equatorial position and the molecule is therefore irregular
tetrahedral.
In ClF3., the two lps may be axial-axial (Fig 1.6(c)(i)), or axial-
equatorial (Fig 1.6(c)(ii)), or equatorial-equatorial (Fig 1.6(c)(iii))
positions. As the axial position will result in maximum repulsion hence
the axial position for the lp is ruled out. Thus the molecule will have T.
shaped geometry, according to the Fig. 1.6(c)(ii).
Similarly, due to reduced lp-lp repulsions and a larger volume that
a lp can occupy at equatorial positions, the [ICl2]- ion will be linear. The
three lps occupy the three equatorial positions, leaving the axial positions
for the Cl atoms (Fig. 1.6(d)).
(I) (II)
(b) SF4, Irregular tetrahedral
10
(c) ClF3, T-Shaped
4. This theory can not explain the shapes of molecules which have
highly polar bonds.
11
Check Your Progress-1
Notes: (i) Write your answers in the space given below;
(ii) Compare your answers with those given at the end of the unit.
(a) Identify and write the shapes of the following molecules.
(i) BeCl2.....................................(iv)
ClF3........................................ (ii)
PCl3.......................................(v)
XeF2........................................
(iii) SF4.........................................(vi)
BrF5........................................ (b) Arrange the following
species in the order of increasing bond-angle, considering the repulsive
forces due to lone pair:
NO2, NO2 and Θ NO2
>---------------->-------------->------------
We know all the systems want to be in a stable state, and the stable
state is one in which it has the minimum possible energy. Same is true for
the stereochemistry or the geometry of a molecule. The VSEPR theory
considered that the most stable configuration of a molecule is one in
which repulsive forces between the valence electron-pairs is minimum. In
contrast, the molecular orbital theory (MOT) considers that the stable
geometry of a molecule can be determined on the basis of the energy of
molecular orbitals formed as a result of linear combination of atomic
orbitals (LCAO). In 1953 A.D.Walsh proposed a simple pictoral-
approach to determine the geometry of a molecule considering and
calculating the energies of molecular orbitals of the molecule.
12
The basic approach is to calculate the energies of molecular
orbitals for two limiting structures, say linear or bent to 90 o for an AB2
molecule, and draw a diagram showing how the orbitals of one
configuration correlate with those of the other. Then depending on which
orbitals are occupied, one or the other structure can be seen to be
preferred. By means of approximate MO Theory implemented by digital
computers, this approach has been extended and generalized in recent
years.
13
Fig. 1.7
14
(Angle θ)
For an AB2E molecule the results are ambiguous, because the trend
in the energy of the 2a1 orbital approximately offsets that of the 1b2
orbiral.
For AB2E2 molecules, the result should be the same as for AB2E.
Since the energy of b1 orbirtal is independent of the angle. Thus it is not
clear in this approach that AB2E2 molecules should necessarily be bent,
but all known ones are.
15
The H2O Molecule:
Fig. 1.9
16
BeH2 - Molecule
The simplest AB2 molecule in Period 2 is the transient gas-phase
BeH2 molecule (BeH2 normally exists as a polymeric solid), in which
there are four valence electrons. These four electrons occupy the lowest
two molecular orbitals. If the lowest energy is achieved with the molecule
angular, then that will be its shape. We can decide whether the molecule
is likely to be angular by accommodating the electrons in the lowest two
orbitals corresponding to an arbitrary bond angle in Fig. 1.7. We then
note that the HOMO decreases in energy on going to the right of the
diagram and that the lowest total energy is obtained when the molecules
is linear. Hence, BeH2 is predicted to be linear and to have configuration
1 g2 2 u2 . In CH2, which has two more electrons than BEH2, three of the
CH4 - Molecule
Methane, CH4, has eight valence electrons. During bonding, for
orbitals [a1g (2s) and t1u (2p)] of carbon, and one [a1g (1s)] orbital of each
17
four hydrogen atoms take part. Overlapping of these eight orbitals, eight
molecular orbitals are formed, the four bonding (2σg or 2a 1 and 2tσ or
2t1) and the four antibonding (2σg* and 2t*σ). The eight valency
electrons of CH4 molecule are distributed in the four bonding molecular
orbitals (Electronic Configuration, 2 12 2t1b ). In the tetrahedral geometry
due to overlapping with the orbitals of hydrogen atom the energy of 2a1g
and 2t1u orbitals is considerably reduced. In contrast, in the distorted
geometry, comparatively less overlapping of t 1u orbitals with the
hydrogen orbitals (as compared to that in the tetrahedral geometry) the
energy of 2t1 molecular orbitals increases. Thus the geometry of CH4
molecule is symmetrical tetrahedral, rather than a distorted tetrahedral.
SF4 - Molecule
In the valence shall of sulphur atom, in SF4 molecule, in addition to
3s (α1g) and 3p (t1u) orbitals, 3d (t2g and eg) orbitals are also present.
During the bonding, 2pz orbital of each of the four fluoring atoms take
part. As a result for bonding (2a1 and 2t1) and four antibonding (2 1* 2t1* )
molecular orbitals formed; while the d-orbitals [α1(dz2), b1(dx2 - y2) and t2
(dxy, dxz, dyz)] are present as non-bonding molecular orbitals. Ten valency
electrons of SF4 molecule remain distributed in the four bonding and one
non-bonding molecular orbitals, resulting in 2 12 ,2t1b . 3a12 configuration.
As in the distorted geometry, overlapping of 2t 1 orbitals is comparatively
greater (thus reducing their energy) and the filling in 3α1 orbital
considerably reduce the energy of the system as compared to that in the
regular tetrahedral structure. Hence SF4 molecule has a distorted
tetrahedral geometry, rather than a regular tetrahedral structure.
18
Check Your Progress 2
Notes:1. Write your answers in the space given below.
2. Compare your answers with those given at the end of this
unit.
(a). Predict the shape of an H2O molecule on the basis of a
Walsh Diagram for an AB2 molecule.
-----------------------------------------------------------------
-----------------------------------------------------------------
-----------------------------------------------------------------
-----------------------------------------------------------------
(b) Is any AB2 molecule, in which A denotes an atom of a
period 3 element, expected to be linear? If so, which
-----------------------------------------------------------------
-----------------------------------------------------------------
-----------------------------------------------------------------
-----------------------------------------------------------------
1.4 d - p BONDS.
There are several structural phenomena that have traditionally been
attributed to the formation of d - p Bonds. Recent work has raised
some doubts. The phenomena in questions are exemplified by:
1. The fact that for amines such as (R3Si)2 NCH3, (R3Si)3 N and
(H3Ge)3 N, the central NSi2C, NSi3 and NGe3 skeletons are planar.
19
Recent re-examinations of these phenomena by both theoretical
and experimental methods together with earlier arguments now suggest
that the d - p contributions to these effects are at best small. Thus, in
reading literature written prior to 1985, where such interactions are often
accorded great importance, one should now be sceptical of all but the
facts themselves.
20
ammine oxide, phosphine oxide presents a strong evidence of the
presence of d - p bond, in a very high stability of P = O.
Similarly the fact that almost all t-phosphines are readily oxidised
into R3P = 0, also indicates that d- p bond is present in the P = O
bonding. This is supported by the lower dipole moment of triethyl
phosphine oxide (1.4 x 10-3 Cm. cf 16.7 x 10-3 Cm. of trimethyl amine
oxide), higher dissociation energy of P = O bond (500-600 KJ, cf 200-
300 KJ of NO bond) and the smaller P-O bond lengths in phosphoryl
compounds.
21
Methyl isothicyanate Silyl isothiocynate
(one lp on N; Angular) lp used in bonding, Linear
(i) The N - S bond length in N SF3 indicates. The bond order = 2.7
indicating d - p bonding:
Thiazytrifluoride
N - S bond length = 141.6 pm; Bond order = 2.7
(cf N - S = 174 pm, b.0 = 1, N = S = 154 pm; b.0 = 2)
(ii) In S4N4F4 also there is indication of d ה- p הbonding (compare with
S4H4N4):
22
(ii) In diphenyl phosphonitrilic fluoride, there is evidence of הbonding
in the ring:
Et3NO.
Ans: (i) ------------------------------- (ii)-----------------------
(iii) -----------------------------
(b) Which are the evidences in favour of d-p bonding
in R3PO molecule?
23
1.5 BENT'S RULE AND ENERGETICS OF HYBRIDISATION:
BENT RULE
24
volume of the bonding pair when held tightly by an electronegative
substituents. Strong, s-rich covalent bonds require a larger volume in
space to bond. Thus double bonded oxygen, despite the high electro
negativity of oxygen, seeks s-rich orbitals because of the shortness and
better overlap of the double bond. Again, the explanation, whether in
purely s-character terms (bent's rule) or in larger angular volume for a
double bond (VSEPR), predicts the correct structure.
25
Consider the cyclic bromophosphate ester.
1. The large bromine atom has diffuse orbitals that overlap poorly
with the relatively small phosphorus atom. Thus, even though the
bromine is less electronegative than the oxygen, it probably does
not form as strong a covalent bond.
26
concentrate in orbitals with strong covalently matched electro
negativities and good overlap.
Energetics of Hybridisation:
According to hybridisation model, bond directions are determined
by a set of hybrid orbitals on the central atom which are used to form
bonds to the ligand atoms and to hold unshared pairs. Thus AB2
molecules are linear due to the use of linear sp hybrid orbitals. AB 2
molecule should be equilaterally triangular, while AB2E molecule should
be angular, due to use of trigonal sp2 hybrids. AB4, AB3E and AB2E2
molecule should be tetrahedral, pyramidal and angular, respectively,
because here sp3 hybrid orbitals are used.
These cases are, of course, very familiar and involve no more than
an octet of electrons.
For the AB5, AB4E, AB3E2 and AB2E3 molecules the hybrid must
now include orbitals in their formation. The hybrid orbitals used must be
of the sp3dz2 leading to TBP geometry and Sp3dx2-y2 leading to SP
geometry. There is no way to predict with certainty which set is preferred,
and doubtless that difference between them connot be great, since we
27
know experimentally that AB5 molecules nearly all have TBP structures,
the same arrangement is assumed for the AB4E cases, and so on. Even
this adhoc assumption does not solve all difficulties, since the position
preferred by lone pairs must be decided and there is no simple physical
model here (as there was in the VSEPR approach) to guide us. A
preference by lone pairs for equatorial positions has to be assumed. With
these assumptions, a consistent correlation of all structures in this five-
electron-pair class is possible.
For AB6 molecule, octahedral sp3d2 hybrids are used. For AB4E2
molecule; there is nothing in the directed valence theory itself to show
whether the lone pairs should be cis or trans. The assumption that they
must be trans leads to consistent results.
28
Perhaps it is surprising that by going to the opposite extreme,
namely by omitting all consideration of d orbitals, but still adhering to the
concept of directed orbitals it is again possible to rationalize many of the
principal features of the structures of main group.
Figure 1.10
29
1.5.1 Third and Fourth Groups Halides
For promoting an atom to hybridised excited state energy is
required. But when the hybrid orbitals give very strong bonds, the
energy gained from bonding may be used for excitation. For
example, when carbon forms four covalent bonds, although there is
a promotion energy from Is22s22p2 ls22s12p3, this is independent
of the hybridization to the valence state :
of the central atom orbitals with orbitals of chlorine atoms. Hence, in the
compounds of heavy elements bonds are weaker, compared to that of the
30
light elements. Because of this less effective overlapping, the heavy
elements utilise pure p-orbitals in bonding and letting the lone-pair 'sink'
into a pure s-orbital. Hence, the stable chlorides of thallium and lead are
TlCl and PbCl2.
Table 1.2: Bond angles in the hydrides of Groups VA (15) and VIA (16)
NH3 = 107.2o PH3 = 93.8o AsH3 = 91.8o SbH3 = 91.3o
OH2 = 104.5o SH2= 92o SeH2 = 91o TeH2 = 89.5o
31
the central phosphorus atom. From the standpoint of this energy factor
alone the most stable arrangement would be utilizing pure p-orbital in
bonding and letting the lone pair "sink" into a pure s-orbital. Opposing
this tendency is the repulsion of electrons, both bonding and nonbonding
(VSEPR). This favours an approximately tetrahedral arrangement. In the
case of the elements N and O the steric effects are most pronounced
because of the small size of atoms of these elements. In the larger atoms,
such as those of P, As, Sb, S, Se and Te, these effects are somewhat
relaxed, allowing the reduced hybridization energy of more p character in
the bonding orbitals to come into play. The molecule is thus forced to
choose between higher promotion energies and better overlap for an-s-
rich hybrid, or lower promotion energies and poorer overlap for an s-poor
hybrid. (s-character: sp3 (25%)<sp2(-33%)<sp(50%)); s-rich means>25%;
s-poor means<25%)
32
1.5.4 Apicophilicity
Good example of the effect of the differences in hybrid bond
strengths are shown by the bond lengths in MXn Molecules with both
equatorial and axial constituents. (Table 1.3)
Table 1.3
req(pm) rax(pm)
PF5 153.4 157.7
PCl5 202 214
SbCl5 231 243
SF4 154 164
ClF3 159.8 169.8
BrF3 172.1 181.0
33
indicating less than 5% s character, but the H-C-H bond angle is larger
and the C-H bond has more s character. The bond angles in the other
fluoromethanes yield similar results.
34
aspects of the subject, to contrast, inorganic chemistry has a wide variety
of structural types to consider, and even for a given element there are
many factors to consider. Inorganic chemistry has been, and to a large
extent still is more concerned with the static structure of reactants or
products than with the way in which they interconvert. This has also been
largely a result of the paucity of unambiguous data on reaction
mechanisms. However, this situation is changing. Interest is increasingly
centring on how inorganic molecules change and react. Most of this work
has been done on coordinate chemistry, and much of it will be considered
later on, but a few simple reactions of covalent molecules will be
discussed here.
One might argue that above equation does not represent a reaction
because the product is identical to the reactant and no bonds were formed
or broken in the process. Leaving aside, the process illustrated above is of
chemical interest and worthy of chemical study.
35
Because these molecules are non superimposable upon their mirror
images (i.e. they are chiral) they are potentially optically active, and
separation of the enantiomers is at least theoretically possible.
Racemization of the optically active material can take place as shown in
mechanism of NH3. It is of interest to note that the energy barrier to
inversion is strongly dependent on the nature of the central atom and that
of subsequent. For example, the barrier to inversion of methyl propyl
phenylphosphine is about 120 MJ Mol-1. This is sufficient to allow the
separation of optical isomers, and their racemization may be followed by
classical techniques. In contrast, the barrier to inversion in most amines is
low (-40 KJ mol) with such low barriers to inversion, optical isomers
cannot be separated because racemization takes place faster than the
resolution can be affected. Since traditional chemical separations cannot
effect the resolution of the racemic mixture, the chemist must turn to
spectroscopy to study the rate of interconversion of the enantiomers.
36
bipyramidal arrangements are related to each other by simple rotation, the
entire process is called a Berry pseudorotation. Note that the process
can take place very readily because of the similarity in energy between
trigonal bypyramidal and square pyramidal structures.
37
side attack takes place because there is retention of configuration. In
either case, the common inversion or the less common retention, there is a
contrast with the loss of stereochemistry associated with a carbonium ion
mechanism.
38
Check Your Progress-5
Notes: 1. Write your answers in the space given below.
2. Compare your answers with those given at the end of this unit.
(a). During atomic inversion of amines, separation of optically active
isomers is not possible: because -
...........................................................................................................
............................................................................................................
(b). During Berry Pseudorotation process in PF5, the mechanism is
believed to take place through.
............................................................................................................
............................................................................................................
(c). Solvolysis (Alcoholysis) of chlorodialkyl phosphineoxide proceeds
with inversion of configurations of phosphorous atom, when the
entering and leaving groups are -
............................................................................................................
............................................................................................................
After going through this unit, you would have achieved the
objectives stated earlier in this unit. Let us recall what we have discussed
so for:
VSEPR theory considers that the geometry of a molecule depends
upon the number of bonding and nonbonding electron pairs in the
central atom. These arrange themselves in such a way that there is
a minimum repulsion between them so that the molecule has
minimum energy (i.e. maximum stability).
39
The repulsive force between the electron pairs very as:
(lp - lp) > (lp - bp) > (bp - bp)
Thus, the more that number of lone pair on a central metal atom,
the greater is the contraction caused in the angle between the
bonding pair. Hence, the bond-angle in CH4 (4bp + Olp) is 109o28',
in NH3 (3bp + lp) is 107o and H2O (2bp + 2lp) is 105o. Similarly.
BCl3 is triangular, but SO2 is angular; PCl5 is trigonal bipyramidal,
but SF4 is irregular tetrahedral; ClF3 is T-shaped, while XeF4 is
square planar.
40
CH2F2, the F-C-F bond angle is less than 109.5o indicating less
then 25% s-character in C-F bond, but the H-C-H bond angle is
larger indicating C-H bond has more than 25% s-character.
41
the inversion of umbrella in a high wind. The energy barrier to
inversion is strongly dependent on the nature of the central atom
and that of substituents. Hence the separation of optical isomers
and their racemization is possible only in such case which have
values of energy barrier sufficiently high (e.g. methylpropylphenyl
phosphine, 120 KJ mol-1).
+
(b) NO2 > .NO2 > -NO2
42
much less, indicating that the molecule is angular. Since in a
linear molecule 3a1 orbital remains non-bonding (i.e. has
very high energy).
(b) (i) The dipole mement has low value (14.6 x 10-3 Cm).
(ii) The bond dissociation energy is high (500-600 KJ).
(iii) P-O bond length is short.
43
UNIT - 2 METAL LIGAND BONDING
Structure
2.0 Introduction
2.1 Objectives
44
2.0 INTRODUCTION
45
a group of two (eg) of higher energy. The nature of the splitting
determines the distribution of electrons among orbitals and hence leads to
the interpretation of magnetic and spectroscopic properties, and is often
very useful in the discussion of distorted structures, thermodynamic
spectral and magnetic properties. The MOT (Molecular Orbital Theory) is
most comprehensive of all the theories, was developed by Van Vleck
(1935) . CFT and MOT apparently give similar results. In practice, thus
modified CFT in which allowance is made for the overlap of the metal
and the ligand orbitals is preferred. The theory is then called 'the adjusted
crystal field theory' (ACFT) or the ligand field theory (LFT) in which the
simplicity of CFT is retained, but the M-L and -bonds are included .
46
2.1 OBJECTIVES
The main aim of this unit is to study nature of metal - ligand bond
and the mechanism of its formation. After going through this unit you
should be able to :
* describe the limitations of crystal field theory (CFT);
* discuss the mechanism of metal ligand bond - formation according
to MOT, for octahedral , tetrahedral and square planar complexes,
* identify the similarities between CFT and MOT , and
* discuss the ligand field Theory (LFT) of metal Ligand bond, as an
adjusted crystal field theory.
Crystal field theory (CFT) was developed (Bethe , 1929 and Van
Vleck , 1932) from 'electrostatic theory ' (Van Arkel , de Boer and Garric,
1932 ), which, considering ligands as point negative charge or point -
dipole works out the effect of the ligand field (Orderly arrangement of the
ligand around the central metal ion , similar to that in an ionic crystal) on
the electronic states of the metal. CFT does not consider mixing or
overlapping of ligand orbitals with those of metal ion , but calculates how
the repulsive effect of electronegative electrical potential field of the
ligands splits d - orbitals of the metal ion into groups of orbitals
(Crystal Field Splitting ) due to loss of the degeneracy .
47
According to this theory the physical and chemical properties of
complexes depend upon the energy of d - orbitals of metal ions , ie crystal
field splitting (CFS) and crystal field stabilisation energy (CFSE) . On the
basis of these only , this theory explains the bonding ability of ligands
(i.e. spectrochemical series) stability of metal complexes, their magnetic
properties (i.e. low-spin and high spin complexes); and the reactivity of
complexes and their thermodynamic properties . But this theory could not
explain the covalent character and the properties based on this character
of the coordinate - bond (i.e. a semipolar bond), thus:
48
(3) ESR , NQR and NMR spectra
ESR and NMR spectra of various complexes (IrCl62-, PtX42-, PdX42-
etc.) and NQR (Nuclear Quadrapol Resonance) spectra of CoCl42-
clearly indicate varying degree of covalency in these complexes ,
but CFT has no room for this character .
(5) Bonding
The CFT can not account for bonding in complexes .
49
Check Your Progress - 1
Notes : (i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of the
unit.
The molecular orbitals are filled in the same way as the atomic
orbitals , following the Aufbau and Pauli's Exclusion Principles. Thus , a
molecular orbital, like an atomic orbital , can contain a maximum number
of two electrons and the two electrons have opposite spins.
50
nucleus, an electron in a molecular orbital is influenced by two or more
nuclei depending upon the number of atoms contained in a molecule.
= A+ B .........................................(2.1)
* = A- B .........................................(2.2)
51
words, the molecular orbital represented by has a lower energy than
either of the atomic orbitals represented by A and B . This orbital ,
therefore leads to the formation of a stable chemical bond and is,
therefore, termed as a 'bonding molecular orbital'.
( *)2 = ( A - B)2 = A2 + B2 - 2 A B
52
signifies that the orbital is symmetrical about the molecular axis and (1s)
indicates that it is formed by the combination of 1s atomic orbitals.
the atoms are added, the probability density function for the bonding MO
i.e. 2 MO is obtained. It is shown by solid lines. It is clear from the
following figure that there is greater probability of finding the electron
between the two nuclei than for separate atoms (Fig. 2.4).
53
For antibonding MO, the picture is quite different. It is formed by
subtraction and he probability density of the two atomic orbitals get
cancelled in the centre so that there is no probability of finding the
electrons in the region overlap, i.e. between the two nuclei, as shown in
the following figure (2.5)
Zero Probability
Fig. 2.5 : Difference combination of wave-function
54
metal ion with the ligand group of orbitals matching symmetry in an
octahedral complex (Fig. 2.7).
55
2.8). Using the steps given above the six metal - ligand -molecular
orbitals can be constructed.
All the nine atomic orbitals have been grouped into four
symmetry classes which are given below:
4s A1g, or a1g; 4px, 4py, 4pz T1u or t1u, 3dx2-y2
3dz2 Eg, or eg; and 3dxy, 3dyz, 3dzx T2g or t2g
in which ligands σ-orbitals (along the +x, -x, +y, -y, +z and -z axes
have been represented as σx, σ-x. σy, σ-y, σz and σ-z respectively).
These σ-orbitals, in order to form six metal-ligand σ-bonds or
MO's will overlap more effectively with only those metal ion
valence AO's that are having their lobes along the axes (i.e., along
the metal ligand direction). Quite evidently, such AO's are 4s, 4px,
4py, 4pz, 3dz-2 and 3dx2-y2, since these orbitals have their lobes lying
along the axes along which the six σ-orbitals of the six ligands are
56
approaching towards the central metal cation to form six metal-
ligand σ-bonds.
The remaining three AO's namely 3dxy, 3dyz and 3dzx do not
participate in σ-bonding process, since these have their lobes
oriented in space between the axes. Thus these orbitals remain non-
bonding and hence are called non-bonding orbitals.
(a) Since 4s orbitals has the same sign in all directions, the linear
combination of ligand σ-orbitals which can overlap with 4s orbitals
is: σx+ σ-x+ σy+ σ-y+ σz+d-z. This linear combination is represented
by a which in its normalised form, is given by:
a
1
x ó -x y y z z ...............A1g or a1g
6
a
1
x - z ..................Eg or eg
2
57
Similarly σy-σ-y and σz-σ-z are the linear combination of
ligand σ-orbitals that overlap with 4py and 4pz atomic orbitals
respectively. Thus:
y
1
y - y ..................Eg or eg
2
z
1
z - z ..................Eg or eg
2
(c) Since one opposite pair of lobes of 3dz2-y2 orbital has a + sign and
the other has - sign, the linear combination of ligand σ-orbitals for
this orbitals is: σx+ σ-x- σy σ-y. Thus
2
x y 2
1
x x y y ..................E1u or e1u
2
(d) To find the ligand σ -orbitals combination for 3dz2 orbital poses
some difficulty. The analytical function for3dz2 orbitals is
proportional to 3z2-r2. The proper σ-orbital combination is easily
written down by substituting x2+y2+z2 for r2 in 3z2-r2. Thus 3z2-
r2=3z2-(x2+y2+z2)=2z2-x2-y2. Consequently the proper combination
for 3dz2 orbitals is:
2 z z x x y y 2 z 2 z x x y y
Thus,
z2
1
2 z 2ó -z x x y y ..................T1u or t1u
2 3
58
a 2
1
σ x ó- x σ y σ y σz σ z
6
x2
1
z - z
2
z2
1
2 z 2 z x x y y
2 3
59
(d) Overlap of metal 3dz2-y2orbital (eg symmetry orbital) with a group
ligand σ-orbitals (eg symmetry).
x 2 y2
1
σ x σ x σ y σ y
2
Fig. 2.9 Construction of LGO's in octahedral complexes.
60
Thus we see that the combinations of six central metal
atomic orbitals with six ligand σ-orbitals give six σb and six σ*
molecular orbitals in an octahedral complex. It is thus obvious that
on adding twelve molecular orbitals (6σb- and 6σ*-MO's) to the
three non-bonding AO's viz. 3dxy, 3dyz, 3dzx we get in all fifteen
orbitals potentially available for electron filling.
4. Molecular Energy Diagram
The molecular orbitals thus formed in step 3, when arranged
in the order of increasing energy, we get molecular energy level
diagram. This can be obtained considering the following principles:
(i) Coulombic energies are in the order (legends are electronegative
than the metal ion): σligand < ligand <3d <4s <4p.
(ii) The mixing of the metal and the ligand group orbitals is
proportional to the overlap of the metal and ligand orbitals, and is
inversely proportional to their coulombic energy difference.
(iii) Bonding σ MOs are more stable than the bonding orbital and
therefore, the antibonding σ*MOs are less stable than the
antibonding * orbitals.
(iv) The bonding orbital lie closer to the LGOs, the antibonding
orbitals are closer to the metal orbitals due to the electronegativity
differences between the metal ion and the ligands atoms.
As the 4s and 4p orbitals can have a better overlap with
LGOs than the 3d orbitals can have with the LGOs, the a 1g and t1u,
MOs are at the lowest energy (corresponding a1g* and t1u* go to the
highest energy levels). The eg and eg* orbitals derived from the eg
orbitals of CFT, interact less with the LGOs due to a poorer
overlap, while the t2g orbitals remain nonbonding in a σ only
picture and are not displaced. The energy level diagram is given in
Fig. 2.10 for the octahedral complexes.
61
Fig. 2.10: MO energy level diagram for an octahedral
complex with no bonding.
As can be seen in Fig. 2.10, the 15 molecular orbitals are
arranged in 7 energy levels. As the energies of all the orbitals in a
symmetry group are equal (i.e. degenerated), out of these seven
energy levels, three are triply degenerated (i.e. T1u, T2g and T1*u).
two are doubly degenerated (i.e. Eg and Eg*) and the remaining
two are monodegenerated (i.e. Alg and A*lg). These energy levels
are arranged as follows:
A1g < T1u < Eg < T2g < Eg* < A*lg < T1u*
Bonding MO's Non-bonding MO's Antibonding MO's
62
5. Distribution of electrons in the Molecular Orbitals
As has been mentioned above if a MO is near in energy to
the energy of the ligand orbitals, it would have more of the
character of the ligand. Thus six σb-MO's (i.e. σsb, σx2, σy2, σzb σx2-y2
and σz2 MO's) which are nearer the energy level of the ligands, are
occupied mainly by the ligand electrons. In other words the
electrons in the six σb-MO's are mainly localised on ligand orbitals,
since σ-orbitals of the ligands are more stable than the metal
orbitals. Conversely, electrons occupying any of the six σ *-MO's
are to be considered mainly metal ion electrons. Electrons in t 2g set
of orbitals will be purery metal ion electrons when there are no
ligand orbital.
Further, the crystal field splitting energy ( o or 10 Dq) in an
octahedral complex, according to MOT, is the difference in energy
between the t2g(dxy,dyz, and dzx orbitals) and eg*(σx2-y2* and σz2*
MO's) energy levels.
In case of weaker ligands such as F-ion, the energy
difference, o between the t2g set eg* set is smaller than P (i.e.
2
o<p) and hence the lowest-energy antibonding MO's namely σx -
2
y * and σz2* have approximately the same energy as the non-
bonding AO's: 3dxy, 3dyz and 3dzx (t2g set). Consequently spin free
(or high spin) complexes are formed. However, the strong(er)
ligands such as NH3 molecules split the σ-bonding MO's more
widely and the energy difference, o between the t2g-set of non-
bonding AO's (3dxy, 3dyz and 3dzx) and eg*-set of MO's (σx2-y2* and
σg2*MO's) is greater than the electron pairing energy. P (i.e. o >
P). Hence spin paired (or low spin) complexes are formed. For
example Co(III) complexes in an decahedral stereochemistry, in
63
all have 18 valence electrons, 12 electrons from six ligands and 6
from d-orbitals in Co3+ ion.
The distribution of 18 electrons in [CoF6]3- which contains
weak (er) ligands viz. F ions (i.e. it is a high-spin complex) takes
place in various orbitals according to the above scheme will be as
follows:
(σs)2, (σx)2 = (σy)2 = (σz)2, σ(x2-y2)2 = (σz2)2, (3dx)2 = (3dyz)1 =
(3dxz)1 = σ*(x2-y2)1 = σ*(z2)1
Hence it will be paramagnetic due to four unpaired electrons.
While, the distribution of electrons, in [Co(NH3)6]3+ which contains
strong(er) ligans viz. NH3 molecules (i.e. it is a low-spin complex)
takes place in various orbitals as follows:
(σs)2, (σx)2 = (σy)2 = (σz)2, σ(x2-y2)2 = (σz2)2, (3dxy)2 = (3dyz)2 =
(3dxz)2
Thus the complex is diamagnetic, due to all paired electrons.
2.3.2 Tetrahedral Complexes
The method used for the construction of molecular orbital energy
level diagram for the octahedral complex, may also be used for the
construction of molecular energy diagram for tetrahedral complexes. Out
of the nine valency orbitals of the metal ion, the orbitals matching to the
Td-Symmetry are s (a1g) and p (t1u). In addition to this, out of the five d-
orbitals, three, the t2g (dxy, dxz and dyz) orbitals are also suitable for the σ-
bonding. Thus the combined symmetry of p(t1u) and d(t2g) orbitals is
generally expressed by T2(Cf the character table for Td symmetry).
64
As a result, three triply degenerated energy levels of molecular orbitals
will be formed; one the group of bonding molecular orbitals, the other
one, the group of slightly anti-bonding molecular orbital and the third one
the group of completely anti-bonding molecular orbitals. (Fig. 2.11).
65
2.3.3 Square Planar Complexes
The square planar complexes, ML4 have D4h symmetry. In these
complexes five d-orbitals of the metal ion, loosing their degeneracy, split
into the four groups of symmetry a mono degenerate a 1g (dz2), a doubly
degenerate eg (dxy and dyz) and the remaining two mono-degenerate
b2g(dxy) and b1g(dx2-y2) orbitals. Similarly, metal ion p(t1u) orbitals also
loose their degeneracy and split into two groups, a monodegenerate
a2u(pz) and a doubly degenerate (px and py) symmetry orbitals.
The four ligands present on the two x and y axes give ligand group
of orbitals (LGO) of a2g, b1g and eu symmetry orbitals. (Fig. 2.12)
66
Fig. 2.13: Molecular Orbital Energy Level Diagram in a
Square Planar Complex.
67
Check Your Progress - 2
Notes : (i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of
the unit.
(a) Name the metal orbitals and their symmetry groups suitable for σ-
bonding in metal complexes of following stereochemistry along
with the LGO's of matching symmetry:
(b) E (cf crystal field splitting in CFT) is the difference between the
68
the t2g symmetry orbitals form the non-bonding energy level in the
complex, while the anti-bonding eg, E*g, form the higher energy level
above the T2g level. (Fig. 2.10)
Thus the results of both CFT and MOT are same as far as d-
bonding is concerned. Only the mechanisms are different in these two
theories. While the cause of o (CFS) in CFT is the electrostatic
repulsion, according to MOT this results overlap of the metal orbitals
with the ligand orbitals. There has, of course, been no change in o which
is any way an experimental quantity; all that has changed is the
interpretation of it.
69
1. M(d ) L(p ) bonding
In which d electrons of the metal ion are donated to the
vacant p orbitals of the ligand (i.e. back bonding). Such bonds
are formed by the metals, situated towards the end of a transition
series in their lower oxidation states with the unsaturated ligands
e.g. CO, NO2-, CN-, RNC, NO etc. (Fig. 2.14)
70
Fig. 2.15: M(d ) L(d ) bonding
71
Remaining two steps involve in the adjustment of -bonding and
anti-bonding molecular orbitals in the σ-molecular orbitals energy level
diagram (Fig. 2.10) and (v) the redistribution of electrons in the modified
MO energy level diagram after adjusting -bonding and anti-bonding
molecular orbitals.
1. Metal Orbitals
In the Octahedral complexes, the metal orbitals suitable for
-bonding may be of t2g or t1u symmetry. As the orbitals of t1u
symmetry (i.e. p orbitals) if used for -bonding will weaken -
bonding, hence the t2g orbitals of metals are most suitable for M
L -bonding.
2. Ligand Orbitals
For formation of the -bond, the ligand can use (i) a p-
orbital perpendicular to the σ-bond axis (e.g. Cl-, F-, OH-) or
(ii) a d orbitals (e.g. PH3, PR3, AsR3 etc.), or
(iii) an anti-bonding * molecular orbital (e.g. CO, CN-, Py)
3. Formation of LGO's
When the ligand -orbitals is p (p) or d , based on the
symmetry of the metal ion orbital (i.e. t2g), ligand group orbitals
may easily be constructed e.g. in Md -Lp bonding:
We know in an octahedral complex each ligand has two p-
orbitals suitable for -bonding (Fig. 2.18) e.g.-
on x axis In ligand L1 1x, 1y
on -x axis In ligand L2 2x, 2y
on y axis In ligand L3 3z, 3x
on -y axis In ligand L4 4z, 4x
on z axis In ligand L5 5x, 5y
on -z axis In ligand L6 6x, 6y
72
In Fig. 2.19 fot Mp -Lp bonding the overlap of pz orbital
of the metal cation with ligand group p orbitals viz ½ ( y1+ x2-
x3- x4) is shown.
73
Fig. 2.20: LGOs for dxz metal orbitals.
Table 2.1: LGO's matching symmetry with metal t1u and t2g
group orbitals for bonding is an octahedral complex:
74
Bonding -molecular orbitals: t2g = T t 2 g t 2 g
Antibonding -molecular orbitals: *t2g = T t 2 g t 2 g
75
The other type of -bonds are formed by the metal ions
placed at the beginning of a transition series in their higher
oxidation states with the saturated ligands such as F-, Cl-, O--, OH-
etc. This type of -bonding destabilise metal complexes.
76
Fig. 2.22: L M, -bonding.
M L, -bonding:
In this case the net result of -interaction is that the metal t2g-
orbitals are stabilised relative to the eg*-MOs i.e. the metal t2g electrons
will go into the t2gb-MOs which are of lower energy than t2g*-MO's and
the thus the value of o will be increased to o ( 1o< 1o). In this case
ligand exerts a stronger field. A ligand of this type is referred to as an
acceptor ligand because of the presence of empty -orbitals in it and the
-bonding established in such a case is sometimes referred to as metal-
to-ligand (M L) -bonding. Phosphines arsines and CO are important
examples of this type of ligands. Hence their complexes are very stable.
L M, -bonding:
In this case the t2g metal orbitals are de-stabilised relative to eg-
MOS. The electrons of the ligand -orbitals enter the lower t2g*-MOs and
those of the t2g metal orbitals will go to higher t2g* MOs. Since in this
77
case, the -interaction destabilises the t2g-metal orbitals relative to eg*-
MOs, the value of o is diminished to o as shown in Fig. 2.22 ( o> o).
The ligand in this case exerts a weaker field. A ligand of this type is
generally called a donor ligand because of its filled -orbitals. Halide
ions are important examples of this type of ligands and the -bonding of
this type is generally referred to as ligand-to-metal (LM) -bonding.
Such type of -bonding occurs in complexes having metal ions in their
normal oxidation states (especially lower oxidation states). These
complexes are comparatively less stable.
As has been pointed out earlier, ligand field theory was specially
developed to explain the nature of metal ligand bond in metal complexes.
We know, the crystal field theory takes no account of possible covalent
bonding in complexes and regards the bonding as purely electrostatic. But
the physical measurements such as electron spin resonance. NMR and
nuclear quadruple resonance suggest that there is some measure of
covalent bonding also in complexes. It is because of this reason that a
kind of modified form of CFT has been suggested in which some
parameters are empirically adjusted to allow for covalence in complexes
without explicitly introducing covalence into CFT. This modified form of
CFT is often called 'Ligand Field Theory' (LFT).
78
first step is to workout splitting of metal d-orbitals into groups of orbitals
having different energies in symmetry. In the second step it calculates the
effect of -bonding (if it takes place) on the crystal field splitting and the
crystal field stabilization energy (CFSE). Probably, because of this
adjustment, Cotton and Wilkinson have called LFT, 'Adjusted Crystal
Field Theory' (ACFT).
Advantages of LFT
1. As LFT was developed specially to explain metal ligand coordinate
bonding in complexes. Hence it is most successful theory.
79
Check Your Progress - 3
Notes : (i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of
the unit.
80
Out of the four theories proposed, based on quantum mechanics,
the two, VBT and MOT were covalent models, while CFT
considered M-L bond purely electrostatic, similar to that existing in
ionic crystals. However, experimental proofs (NMR, ESR and
Nephclauxetic studies etc) clearly indicated varying degree of
covalence in the M-L bond. Hence, LFT was formulated using the
two most useful theories CFT and MOT. Since the results of CFT
and -bonding in MOT are same in determining splitting of metal
d-orbitals; and as the crystal field splitting energy, E, form the
basis for the explanation of most of the properties of complexes,
LFT was developed by adding -bonding from MOT in CFT, to
account for the covalence in M-L bond. Cotton and Wilkinson
called it 'Adjusted Crystal Field Theory' (ACFT).
81
Metal complexes may have either ML -bonding or LM -
bonding. The first one stabilities the complex, by increasing the
value of E; while the later one destabilize it, as the value of E
decreases.
1.(a) (i) ESR (ii) NMR spectra and (iii) Nephelauxetic studies.
(b) -bonding; since ML -bonding in CN- complexes increases
the value of E, Hence it is at the top of spectrochemical series
(SCS); while LM -bonding in F- complexes very much
reduces E, placing F- at the bottom in SCS.
2. (a)
Metal σ -orbitals Symmetry LGO
(i) Octahedral s and p; dz2 and dx2-y2 a1g and t1u ,eg Ʃa, Ʃt1u
and Ʃeg
(ii) Tetrahedral s, dxy, dyz and dxz a1g, t2g Ʃa, Ʃt2g
(iii) Square dx2-y2, 2
dz , dxy, dyz b1g, 1g , b2g, Ʃb1, Ʃay
planar and dxz eg Ʃb2 Ʃeg
82
(b) (i) Eg* - t2g
(ii) t2* - Eg
(iii) B1g* - A1g
3.(a) (i) ML -bonding
(ii) It increase Crystal Field Splitting Energy E very much.
(iii) [Fe(CN)6]4-
(b)
(i) Names (ii) Symmetry (iii) LGO
dxy 1
2
x1 y 2 x3 y 4
dxz
t2g
1
x5 y1 x3 x6
2
dyz 1
x 2 y 5 x 6 y 4
2
83
UNIT 3 ELECTRONIC SPECTRA OF TRANSITION METAL
COMPLEXES
Structure
3.0 Introduction
3.1 Objectives
84
3.0 INTRODUCTION
The principal new work in the first part of this unit is the problem
of interelctronic repulsions. To see how to take repulsion into account,
you must recall what you have already studied about the basic concept of
interelectronic repulsion for atomic spectra, quantitatively. Then we can
go on to see how repulsions compete with the ligand field when the atoms
and ions are present as a part of a complex.
In the end of the unit we shall try to use these spectra for
assignments of absolute configuration in optically active metal chelates
and their stereochemical information.
3.1 OBJECTIVES :
85
The main aim of this unit is to see how to analyse the electronic
spectra of transition metal complexes, and hence to enrich our
understanding of their bonding. After going through this unit you should
be able to :
describe spectroscopic ground states and their correlation;
explain selection rules for d-d transition;
discuss orgel and Tanabe-Sugano diagrams for splitting of
electronic states in different ligand – fields;
calculate values of dq, B and parameter considering the bands
obtained in the spectra of the complex;
explain charge transfer spectra (both the metal to ligand, and ligand
to metal charge transfer); and
assign absolute configuration of optically active metal chelates
using 'Optical Rotatory Dispersion' (ORD) and 'Circular
Dichroism' (CD).
86
occur at some what higher frequency than d-d transition. Generally,
electronic spectra are of four types :
87
observed generally for the metal ions in low oxidation states in the
ultraviolet region, but are seen many times to tail into the visible
regions, e.g. [Fe (dipy)3]2+.
88
3.3.1 Correlation Diagrams
To develop energy level diagrams of complexes, start is made with
the free ion of dn configuration and then interelectronic repulsions and the
ligand field effects are added to it. Electron – electron repulsion is the
cause of splitting in the terms of electron configuration.
Hence, a 3F state gives 3T1g, 3T2g and 3A2g states whereas the 3P
state is not split and gives 3T1g (P) state (Fig. 3.2). In dn configuration
electron – electron interaction starts.
89
Table 3.1 Splitting of the Terms in a dn ion in Weak Octahedral Field
90
Fig. 3.3 Ground term splitting and energy (in Dq) unit for dn ions in
octahedral field (weak). Number below each level is the degeneracy
of level, number above is the energy.
Table 3.3 The Ground State and Higher Energy Terms for the dnIon
Configuration Ground State Higher Energy Terms
Term
d1, d2 2
D
d2, d8 3
F 3
P, 1G, 1D, 1S
d3, d7 4
F 4
P, 2H, 2G, 3F, 2 x 2D, 2P
3
H, 3G, 2 x 3F, 3D, 2 x 3P, 1I, 2 x 1G,
d4, d6 5
D 1
F, 2x 1D, 2x 1S
4
G, 4F, 4D, 4P, 2I, 2H, 2 x 2G, 2 x 2F,
d5 6
S 3 x 2D, 2P, 2S
91
the energy terms (ground state as well as the excited state) should
be shown (Fig. 3.4 for a d2 ion) and analyzed.
Fig. 3.4 Correlation diagram for d2 system in octahedral field. (a) free
energy terms, (b) terms in a weak field, (c) variations in the field of
intermediate strength, (d) terms in a strong field configurations.
92
of unpaired electrons must not be changed, but this is not quite the same
thing. For example, the transition S2 S1P1 is spin-allowed so long as
the spins of the two electrons in the S1P1 state are + ½ and – ½ (i.e. the
state is a singlet); transition to the triplet state, in which both spins have
the same sign, is forbidden.
93
Breakdown of Laporte's Selection Rule: The mixing of the
orbitals on the metal ion (d-f, d-p), or vibronic coupling can result in the
breakdown of the Laporte's selection rule. Thus if d and p orbitals mix.
= (3d) + (4p),
94
Check your Progress-1
(a) The ground state Terms for the following free ions and their
splitting components in an octahedral field are :
(b) With what the two selection rules are related? Name the
complex in which the rule is violated.
Rule Related with Breakdown
1st Rule ------------- -------------
------------- -------------
2nd Rule ------------- -------------
------------- -------------
95
If one plots the magnitude of splitting of the energy levels with the
increasing ligand field for a dn system, and take into consideration the
spin-orbit coupling and mixing of the different energy states, especially
under a strong field, the Orgel diagram for the ion is obtained. These are
given for the dn ions in Fig. 3.5
Further, the energy level diagram for the d n ion in the tetrahedral
field has the same form as that for the d10-n system in the octahedral field,
except that the tetrahedral field splitting is considerably less (44 per cent
only). When the octahedral and tetrahedral field splittings are plotted in
the same diagram, the Orgel diagram for the system results (Fig. 3.5).
The fig. 3.5 represents Orgel diagram for Co2+(d7) in the tetrahedral
and octahedral fields. Here again we can see the inverse relationship
between these two symmetries. This is because the tetrahedral field, in
fact is a negative octahedral field. In this diagram effects of the mixing of
the terms can be seen.
96
difference in the energy between these terms. For Co2+ these terms are of
two, 4T1 (tetrahedral) and 4T1g (octahedral) levels. The mixing of terms
takes place, just similar to the mixing of molecular orbitals. The energy of
the higher level is incrased, while that of the lower level decreases. In the
fig. (for CO2+) this is represented for the pairs of 4T1g and 4T1 by
diverging lines, in case the mixing does not take place, the state is
represented by dotted lines. This can be seen, in case of tetrahedral, the
absence of mixing brings the energies of two 4T1 terms gradually closer
with the increasing field strength. While in octahedral complexes just
reverse of this is seen. Thus, in tetrahedral complexes the limit of mixing
is high.
97
Dq/B (a)
Dq/B (b)
Fig. 3.6 Tanabe-Sugano diagrams for (a) d2 and (b) d5 ions in
octahedral field.
The Tanabe-Sugano diagrams suffer from the disadvantage that (i)
the diagram depends on C/B ratio; (ii) There is no accurate way to
determine C and B values for the metal ions in complexes.
98
Even though the C and B values for the metal ions in complexes
are lower than those in the free metal ions, the Orgel as well as the
Tanabe Sugano diagrams do not consider this points at all.
The d-d transitions have low intensities. When they are both spin
forbidden and Laporte forbidden, is very low. Substitution in
octahedral complexes, which destroys the centre of symmetry of the
ligand, gives higher absorption. Laporte restriction does not apply to the
tetrahedral complexes due to the absence of the centre of symmetry in the
ligand field. Hence, the tetrahedral complexes of the same ions are more
intensely colored than the octahedral complexes. e.g. [CoCl 4]2- is blue
whereas [Co(NH3)6]2+ pink. Multiplicity forbidden transition bands are
sharp, whereas the multiplicity allowed t2geg transition give a broad
band as the excited state has longer bond lengths and the electronic
transitions are faster than the vibrational transitions.
Tanabe Sugano diagram in a simple form, is expressed in Fig. 3.7
for d6 ion in an octahedral stereochemistry. In these diagrams the ground
state is taken as the abscissa and other energy states are recorded relative
to this abscissa. While the interelectronic repulsion is expressed in terms
of Racah parameters, B and C. The constant B is sufficient to give
information about the energy differences in the levels of same spin-
multiplicity, but for the terms of different multiplicity, both B and C
parameters become necessary. For the energy difference between the
99
ground state F term of free ion having same spin-multiplicity and the
excited P term is 15 B (As is seen in case of d 2, d3, d7 and d8
configurations).
In Tanabe-Sugano diagrams the energy, E and the field strength, B
is expressed in terms of E/B and /B respectively. In Fig. 3.7 C/B = 4.8;
while, in the ions of most of the transition-series B is nearly equal to 1000
cm-1 and C = -4B.
100
corresponding to 1A1g1T1g and 1A1g1T2g as shown by both [Co(en)3]3+
(21400, 29500 cm-1) and [Co(Ox)3]3- (16500, 23800 cm-1) ions.
1
A1g 1T2 g 29600cm 1
1.37
1
A1g 1T1g 21550cm 1
101
Fig. 3.8 Electronic spectra of [Co(en)3]3+ and [Co(Ox)3]3- Complexes.
On fitting this into the Tanabe-Sugano diagram (Fig. 3.7), this ratio is
obtained at / B = 40. From the diagram, the value of E/B obtained for
the transition of lowest energy, is 38. Hence,
21550cm1
1
A1g 1T1g
38
B B
This gives, B = 570 Cm-1, which very much less, than the value of
Bo, for the free Co3+ ion (= 1100 cm-1).
From the value of / B (= 40) and B(=570 cm-1) , the value of
obtained is 23000 cm-1 (Theoretical value, 23160 cm-1).
102
Check Your Progress-2
Notes :(i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of the
units.
(a) (i) In Orgel diagrams...................................................are plotted
against..............................................; while in Tanabe-Sugano
diagrams.............................is plotted against...................................
(ii) Orgel diagrams are suitable for complexes of.........................
fields only, but Tanabe-Sugano diagrams are suitable for.............
B and C Racah parameters represent.....................................while,
represents.......................and is the ratio of .........................
103
Metal-to-Ligand Charge Transfer:
The visible absorption spectra of iron(II) complexes with ligands
containing the –diimine unit
\ /
–N N–
ability increases, the energy of the dxz and dyz orbitals decreases relative
to that to the * (TIM) orbital, causing the t2g * (TIM) charge-transfer
band to move to higher energies.
Ligand-to –Metal Charge Transfer:
Such bands are often prominent in the spectra of complexes in
which there are electrons in π -orbitals of the ligands. The specra of
RuCl62- and IrBr62- (d4 and d5 complexes, respectively) show two sets of
bands that have been assigned to transitions from the weakly bonding -
orbitals on the ligands to the anti-bonding t2g* and eg* orbitals of the
metal atom. In IrBr63- (a d6 complex), the t2g* orbitals are field, and only
the transitions to the eg* orbitals can be observed.
104
lengths. These indicate LM electron transfer, because the difference of
energy between the lowest energy empty molecular orbitals in the metal
ion and the highest filled molecular orbitlas in the ligand is very less
(lesser than 10,000 cm-1).
For charge transfer bands the values of molar extinction
coefficient, , are much higher ( x 500-2000) than that of d-d
transitions( =100).
105
extent of rotation being affected. This variation in sign and magnitude
of rotation with wavelength, which is illustrated in Fig. 3.9, is known as
optical rotatory dispersion. If the rotation rises to a maximum towards
short wavelengths before changing sign, the compound is said to show a
positive cotton effect; the opposite behavior constitutes a negative
cotton effect.
As a matter fact, the rotation of the plane polarized light is due to
different refractive indices n1 and nr, for the left and right circularly
polarized light. Hence, the two components interact differently with the
medium and emerge out of phase. On combination, the plane of
polarized light gets rotated. The variation of the rotation of the plane of
plane polarized light with wavelength (Fig. 3.9) is called the optical
rotatory dispersion, (ORD) and the abrupt reversal of the rotation in the
vicinity of the absorption band is called the Cotton effect.
106
3.8.2 Circular Dichroism, CD
A chiral molecule displays circular dichroism. That is, the
molecule has different absorption coefficients of right and left circularly
polarized light at any given wavelengths. A Circular dichroism spectrum
(a CD spectrum) is a plot of the difference of the molar absorption
coefficients for right and left circularly polarized light against
wavelength. As we see in Fig. 3.10 enantiomers have CD spectra that are
mirror-images of each other. The usefulness' of CD spectra can be
appreciated by comparing the CD spectra of two enantiomers of
[Co(en)3]3+ (Fig. 3.10 (b)] with their conventional absorption spectra (Fig.
3.10(a). The latter show two ligand field bands, just as thought the
complex were an octahedral complex, and give no sign that we are
dealing with a complex of lower (D3) symmetry. That difference,
however, shows up in the CD spectra where an additional band is seen
near 24000 cm-1.
Fig. 3.10 (a) The absorption spectrum of [Co(en)3]3+ and (b) the CD
spectra of the two optical isomers.
Although ORD was used extensively at one time because of
simpler instrumentation, circular dichroism is currently much more
useful. The CD effect because there is differential absorption of left and
right circularly polarized light associated with transitions such as 1A11E
and 1A11A2. The circular dichroism is the difference between the molar
absorptivities of the left and right polarized 1 r , (solid curves in Fig.
3.9). Complexes having the same sign of CD for a given absorption band
will have the same absolute configuration. Hence, CD spectra can be used
107
to relate large families of chiral complexes to the small number of
primary cases, including [Co(en)3]3+, for which absolute configurations
have been established by X-ray diffraction.
Conformation of Chelate Rings
In addition to the dissymmetry generated by the tris (chelate)
structure of octahedral complexes, it is possible to have dissymmetry ion
the ligand as well. For example, the gauche conformation of
ethylenediamine is dissymetric and could be resolved were it not for the
almost complete absence of an energy barrier preventing recemization.
Attachment of the chelate ligand to a metal retains the chirality of the
gauche form, but the two enantiomers can still interconvert through a
planar conformation at a very low energy, similar to the interconversions
of organic ring systems. Thus, although it is possible in principle to
describe two enantiomers of a complex such as [Co(NH3)4(en)]3+, in
practice it proves to be impossible to isolate them because of the rapid
interconversion of the ring conformers.
If two or more rings are present it one complex, they can interact
with each other and certain conformations might be expected to be
stabilized as a result of possible reductions in interatomic repulsions. For
example, consider a square planar complex containing, two chelated rings
of ethylenediamine. From a purely statistical point of view we might
expect to find three structures, which may be formulated M , M and
M (which is identical to M ). The first two molecules lack a plane
of symmetry, but M is a meso form. Corey and Bailar were the first to
show that the M and M should predominate over the meso form.
108
(a) (i) LM charge transfer bands arise due to transfer of charge
from..............................to................................and are exemplified
by.............................complexes.
After going through this unit, you would have achieved the
objectives stated earlier in this unit. Let us recall what we have discussed
so far.
Most of the transition metal complexes are highly colored as they
absorb radiant energy in the visible region of the spectrum.
Transition metal spectra are of four types:
(i) d-d spectra: Which occur in the near IR, visible and UV regions,
and are due to excitation of electrons from the t2g level to e*g
levels largely in the metal itself.
109
(ii) LM charge transfer spectra: Takes place from a MO located
primarily on the ligand to a non-bonding or anti-bonding MO
located primarily on the metal atom.
(iii) ML charge transfer spectra: Involve transitions of electron
from an anti-bonding or non-bonding orbitals, concentrated on
the metal atom, to the anti-bonding orbital located primarily on
the ligands.
(iv) Intraligand transitions: Involve electron transitions from one
ligand orbitals to another ligand orbitral.
In the absence of external field d orbitals of the metal ion are
degenerate and their ground states for dn configuration are:
d1 2
D d6 5
D
d2 3
F d7 4
F
d3 4
F d8 3
F
d4 5
D d9 2
D
d5 6
S d10 1
S
In presence of the external field the degenerate d-orbitals split into
groups of orbitals according to the field strengths. Orgel and
Tanabe-Sugano diagrams represent the ground and excited states of
a given configuration.
110
terms of E/B (B=Racah parameter) against Dq/B, the ground state
of the system being always plotted as abscissa. Thus, they also take
into account of interelectronic repulsion (in the form of B and C
parameters).
The value of and B for a given complex may be calculated by
fitting its observed spectrum into the Tanabe-Sugano diagrams.
The value of Nephelauxetic coefficient (interelectronic repulsion),
is obtained by dividing electronic repulsion constant of the
ORD and CD form the basis for cotton effect (The abrupt reversal
of the rotation in the vicinity of the absorption band), and as a rule
if in analogous compounds, corresponding electronic transitions
111
show cotton effects of same sign the compounds have the same
optical configuration.
(b)
1st rule Spin multiplicity Spin free oh complexes of Mn2+(d5)
2nd rule Redistribution of NiCl42-, Th complex gives more
electrons in a intense absorption than of an Oh
given sub-shell complex.
2(a)(i)In Orgel diagrams energy state E are plotted against field
strength. B; while in Tanabe-Sugano diagrams E/B is plotted
against /B.
(ii) Orgel diagrams are suitable for complexes of weak fields only;
but tanabe-sugano diagrams are suitable for both weak and strong
fields.
(b) B and C Racah parameters of complexes represent inter
electronic repulsion; while nephelauxetic coefficient represent
B
nephelauxetic effect and is the ratio of B and B0 i.e.
Bo
112
(ii) ML charge transfer is seen in acceptor ligands containing
empty low energy orbitals, e.g. CO, CN-, NO complexes. These
bands arise due to transfer of charge from metal t2g orbitals to
anti-bonding orbitals of the ligand.
(b)(i) ORD is the variation in sign and magnitude of rotation of plane
of polarized light with wave length; while CD plots the difference
of the molar absorption coefficients for right and left circularly
polarized light against wave length.
(ii) The absolute configuration in optically active metal chelates may
be assigned using a general rule: if in analogous compounds,
corresponding electronic transition shows cotton effects of same
sign, the compounds have the same optical configuration.
113
M.Sc. (Previous) Chemistry
BLOCK – II
Complexes.
Complexes-1
114
UNIT-4 MAGNETIC PROPERTIES OF
TRANSITION METAL COMPLEXE
Structure
4.0 Introduction
4.1 Objectives
115
4.0 INTRODUCTION
116
4.1 OBJECTIVES
d d
where d and M are the density and molecular weight of the
substance, respectively. For most substances, K, x and xM have negative
values; such substances are weakly repelled by a magnetic field and are
called "diamagnetic". For substances having unpaired electrons that do
not strongly interact with one another, K, x and xM have relatively large
117
positive values; these substances are attracted into a magnetic field and
are called 'paramagnetic."
When a paramagnetic substance is placed in a magnetic field, the
moments of the paramagnetic molecules or ions tend to align with the
field; however, thermal agitation tends to randomize the orientations of
the individual moments. Theoretical analysis of the situation leads to the
relations;
N 2
x Mcorr
3kT
where X Mcorr is the molar susceptibility which has been corrected
both for the diamagnetic contribution to the susceptibility (due to the non
paramagnetic atoms in the sample) and for any small temperature-
independent paramagnetism arising from paramagnetic excited states of
the system. N is Avogadro's number, k is the Boltzmann constant, µ is the
"magnetic moment" of the molecule, and T is the absolute temperature.
By substituting numerical values for N and k, we obtain;
0.125 2
X Mcorr or 2.83 X Mcorr T
T
118
measurements on a number of diamagnetic materials make it possible to
estimate the appropriate correction factors. The diamagnetic susceptibility
for a particular substance can be obtained as a sum of contributions from
its constituent unit: atoms, ions, bonds, etc. The basic assumption
underlying such a procedure, namely, that the diamagnetism associatiated
with an individual atom or other unit in independent of environment, has
been shown to be valid.
N 2 2
xM
3RT
1/ 2
3RTX m
2.84( x M T )1 / 2
N
2
g[ J ( J 1)]1 / 2
119
where J is the total angular momentum quantum number and g is
the Lande splitting factor for the electron, defined as:
J ( J 1) S ( S 1) L( L 1)
g 1
2 J ( J 1)
[4S (S 1) L( L 1)]1 / 2
120
Check Your Progress - 1
121
Table 4.1: Magnetic properties of some complexes of the first-row
transition metals
High spin complexes Low spin complexes
Central No. of d No. of No. of
µ(expt) µ(calc)b µ(expt) µ(calc)b
metal electrons unpaired unpaired
BM BM BM BM
electrons electrons
Ti3+ 1 1 1.73 1.73 - - -
V4+ 1 1 1.68- 1.73 - - -
1.78
V3+ 2 2 2.75- 2.83 - - -
2.85
V2+ 3 3 3.80- 3.88 - - -
390
Cr3+ 3 3 3.70- 3.88 - - -
3.90
Mn4+ 3 3 3.8-4.0 3.88 - - -
Cr2+ 4 4 4.75- 4.90 2 3.20- 2.83
4.90 3.30
Mn3+ 4 4 4.90- 4.90 2 3.18 2.83
5.00
Mn2+ 5 5 5.65- 5.92 1 1.80- 1.73
6.10 2.10
Fe3+ 5 5 5.70- 5.92 1 2.0-2.5 1.73
6.0
Fe2+ 6 4 5.10- 4.90 0 - -
5.70
Co3+ 6 4 - 4.90 0 - -
Co2+ 7 3 4.30- 3.88 1 1.8 1.73
5.20
Ni3+ 7 3 - 3.88 1 1.8-2.0 1.73
Ni2+ 8 2 2.80- 2.83 - - -
3.50
Cu2+ 9 1 1.70- 1.73 - - -
2.20
122
4.3.1 ORBITAL CONTRIBUTION IN MAGNETIC MOMENTS
123
electron pairing energies, (ii) higher LF or MO splittings. The µ at room
temperature is generally lower than µs and cannot be used to determine
the unpaired electrons due to (iii) high spin-orbit coupling constants
which align L and S vectors in opposite directions destroying the
paramagnetism.
Further, (iv) the Curie or Curie-Weiss law does not hold, the
variation of µ with L is complex and depends upon the number of the
electrons present.
Some ions like MnO4-, CrO42- and low spin Co3+ complexes
show temperature-independent paramagnetism (TIP) even though they do
not have any unpaired electron. This is due to the spin-orbit coupling of
the ground state to a paramagnetic excited state under the influence of the
magnetic field. The degree of mixing is independent of temperature but
depends on the applied magnetic field, as the excited state is well
separated from the ground state, whose population does not change with
temperature.
124
the paramagnetic centers are well separated from each other by
diamagnetic atoms. In materials that are not magnetically dilute, unpaired
spin on neighboring atom may couple with each other, a phenomenon
referred to as magnetic exchange. Materials that display exchange
behavior can usually be treated with a modification the Curie-Weiss Law;
C
xM
(T )
where ø is a constant with units of temperature. If the interacting
magnetic dipoles on neighboring atoms tend to assume a parallel
alignment, the substance is said to be ferromagnetic (Fig. 4.1(b)). If, on
the other hand, the tendency is for an anti-parallel arrangement of the
coupled spins, the substance is anti-ferromagnetic.(Fig. 4.1(c)) In any
material that exhibits magnetic exchange, the tendency towards spin
alignment will complete with the thermal tendency favoring spin
randomness. In all cases, there will be same temperature below which
magnetic exchange dominates, this temperature is called the Curie
temperature (TC) if the type of exchange displayed is ferromagnetic and
the Neel temperature (TN) if it is anti-ferromagnetic. The change in
susceptibility as the temperature is decreased below either TC or TN may
be quite dramatic.
Paramagnetism Ferromagnetism Antiferromagnetism
125
Fig.4.2 The magnetic moment of Fe(phen)2(NCS)2
as a functions of temperature.
pairing energy (P): We associate high spin complexes with the condition
P and low spin complexes with P . For complexes in which the
126
4.5 SPIN CROSSOVER
With the change in field strength, change in the magnetic moment
i.e., the change from high-spin to low-spin can be explained in terms of
splitting of electronic states with the field strength, e.g. the Tanabe-
Sugano diagram to these d6 complexes show that near the crossover point
between weak and strong field the difference in energy between the spin-
free (5T2g) and spin-paired (1A1g) ground states becomes very small (Fig.
4.3) within this region, it is reasonable to expect that both spin state may
be present simultaneously and that the degree to which each is
represented will depend on the temperature ( - P = kT). A complex
illustrating these effects is [Fe(phen)2(NCS)2] (Fig. 4.2). At high
temperature a moment consistent with four unpaired electrons is
observed, but as the temperature is decreased, a sharp drop in magnitude
is observed at 175K where the low-spin form becomes dominant. Usually
spin transitions occur somewhat more gradually than in the case shown
here, and reasons for the abruptness observed for this complex, as well as
some residual paranagnetism seen at low temperature have been
discussed extensively.
5
T2g
E
1
A1g
127
In solutions, these systems are fairly straightforward; the change in
magnetic susceptibility with temperature can be interpreted in terms of
the heat of conversion of one isomer to another. However, treatment of
the system as an equilibrium between two spins yields H=3.85 kcal
mol-1 and S = 11.4 for the high spin low spin conversion. On the
other hand, spin crossover in solids is a complex phenomenon because of
cooperative structural changes and changes in the energy separation of
the high-spin and low-spin states with temperature. Thus the magnetism
of Fe(phen)2(NCS)2 change sharply at 174K, as shown in Fig. 4.2
128
4.6 LET UP SUM UP
M
X K
or X M K
d d
where d and M are the density and molecular weight of the substance,
respectively.
xM is the molar susceptibility which has been corrected both for the
diamagnetic contribution to the susceptibility and for any smll
temperature-independent paramagnetism from paramagnetism
excited states of the system, and may be given as,
0.125 2
X Mcorr or 2.83 X Mcorr T
T
129
when values of Avogadro's number, A, Boltzman constant K,
the magnetic moment of the substance, µ and absolute temperature are
substituted.
μ [n(n 2)]1 / 2
130
The observed magnetic moments for the metals in t 2g ground state
are temperature dependent and usually depart from the µs values
due to probably the t2g electron delocalization and lower symmetry
ligand field components.
The Curie's Law states that paramagnetic susceptibility is inversely
proportional to the absolute temperature;
xM = C/T
If the interacting magnetic dipoles on neighboring atoms tend to
assume a parallel alignment, the substance is said to ferromagnetic,
and if, on the other hand, the tendency is for an anti-parallel
arrangement of the coupled spins, the substance is anti-
ferromagnetic.
131
4.7 CHECK YOUR PROGRESS: THE KEY
KM
1. (i) XM
d
2.A (i) High spin d1, d2, d6 and d7 ion complexes, and low spin d4 and
d5 ions.
(ii) For Fe2+ and Co2+ complexes.
E. Between spin free 5T2g and spin paired 1A1g ground states
become very small.
132
UNIT-5 METAL π COMPLEXES
Structure
5.0 Introduction
5.1 Objectives
5.2 Metal Carbonyls
5.2.1 Classification
5.2.2 Isolobal Concept
5.2.3 Methods of Preparation and Properties
5.2.4 Structure
5.2.5 Vibrational Spectra
5.3 Metal Nitrosyls
5.3.1 Neutral NO and NO- Complexes
5.3.2 Complexes of NO+
5.3.3 Pure Nitrosyl Complexes
5.3.4 Nitrosyl Carbonyl Complexes
5.3.5 Nitrosyl Halide Complexes
5.3.6 Nitroso Cyanide Complexes
5.4 Dinitrogen Complexes
5.4.1 Fixation of Nitrogen
5.5 Dioxygen Complexes
5.5.1 Heme Proteins and Transportation of O2
5.5.2 Haemoglobin
5.6 Tertiary Phosphine as Ligand
5.7 Let Us Sum Up
5.8 Check Your Progress: The Key
133
5.0 INTRODUCTION
with the metal ion through LM, ϭ-bond, has vacant π-orbitals, it can
accept lone pair of electrons from metal-ion (if present) to form ML, π-
bonds. This also accounts for the extra stability of metal complexes with
unsaturated ligands. However the latest and the most successful theory of
bonding for metal-complexes Ligand Field Theory (LFT), explained
quantitatively while Mπ-bonding stabilizes, the complex, LM
π-bonding destabilize it. This also explains positions of CN- and F-
ligands in the spectrochemical series.
as they involve both metal carbon ϭ and π-bonds. In this unit we shall
consider the metal carbonyls, anions derived from them, some of their
substitution product, and complexes formed by a few other ligands.
5.1 OBJECTIVES
134
describe metal carbonyls, their classification, methods of
preparation and reactions; with special reference to their structures,
discuss how these complexes, almost without exception, conform
to the effective atomic number rule and isoloble concept,
explain bonding in these complexes in terms of IR spectra;
describe preparation, properties and structures of metal nitrosyls,
discuss dinitrogen complexes and their importance in the fixation
of nitrogen;
explain formation of dioxygen complexes with special reference to
transportation of oxygen by heme proteins; and
describe the nature of complexes with tertiary phosphine as a
ligand.
135
The general formula of the carbonyls may be given as Mx(CO)y
where M is a metal capable of forming carbonyl. Metal carbonyls may be
regarded as parents of number of related compounds such as metal
nitrosyl carbonyl, M (NO)y (CO)x, and metal carbonyl hydrides HxM
(CO)y.
5.2.1 Classification
136
2. When CO is passed over reduced iron at 108o-220o and
pressure of 50 to 200 atom pressure. Fe(CO)5 is formed;
Fe - + 5CO Fe(CO)5
Rhenium, osmium and iridium carbonyls could not be prepared
by direct reactions.
Table 5.1 The binary carbonyls
Electrons needed 13 12 11 10 9 8
to attain noble
gas
configuration
First transition V(CO)6 Cr(CO)6 Mn2(CO)10 Fe(CO)5 CO2(CO)8 Ni(CO)4
series blue solid white solid yellow solid yellow liquid orange solid colourless
(sublimes) (m.p.154o) (b.p.103o) Fe2 (m.p.51o) liquid
(CO)12 black CO6(CO)16 (b.p.43o)
solid black solid
(sublimes)
Second Mo(CO)6 Te2(CO)10 Ru(CO)5 Rh2(CO)8*
transition series white white solid colourless
solid(subli liquid (m.p.- Rh4(CO)12
mes) 22o) orange solid
Ru2(CO)9* Rh6(CO)16
Ru3(CO)12 black solid
orange solid
(m.p.-154o)
Third transition W(CO)6 Re2(CO)10 Os(CO)5 Ir2(CO)8
series white white solid colourless yellow solid
o
solid(subli (m.p.177 ) liquid Ir4(CO)12
mes) (m.p.15o) yellow solid
Os2(CO)9 Ir6(CO)16 red
Orange solid solid
Os2(CO)12
Yellow solid
o
(m.p.224 )
137
b. Indirect synthesis involving the Gringed reagent: job prepared
chromium hexacarbonyl by the action of CO on a mixture of
grignard reagent and anhydrous chromium chloride in ether
solution.
According to Hiber the primary reaction is as follows:
C6H5MgBr + CrCl3 + CO Cr(CO)2(C6H5) + MgBrCl + MgBr2
The unstable intermediate compound is composed with acid
to yield the hexacarbonyl:
3Cr(CO)2 (C6H5)4 + 6H Cr(CO)6 + 2Cr3+ + 12C6H-5 + 3H2
The reactions gives low yield which can be improved by
using high carbon mono-oxide pressure.
138
CrCl3 CO LiAlH y 115
Cr(CO)6 + LiCl + AlCl3
o
2Rul3 + 10CO + 6Ag 175 2Ru(CO)5 + 6Agl
C 250atmpressure
C210
2Mnl3 + 10CO + 2Mg 25 2Mn2(CO)10+ 2Mgl
atmpressure
C
Re2O7 + 17CO 75
Re2(CO)10 + 7CO2
atm
200
139
Properties of Carbonyls
i. The metal carbonyls are crystalline solids, except for nickel
carbonyl and the pentacarbonyls of iron, ruthenium and osmium
which are liquids.
ii. Many are coloured for example: Crystals of cobalt carbonyl are
orange and iron pentacarbonyls is yellow oil and nicked carbonyl is
colourless.
iii. Due to their covalent nature renders them insoluble in water, most
of them are soluble in solvents like CCl4.
iv. Excepting V(CO)6 all the carbonyls are diamagnetic. V(CO)6 is
paramagnetic and its paramagnetic property corresponds to the
presence of one unpaired electron. The metal in carbonyls are in
zero oxidation state.
140
Chemical Properties
1. Substitution Reactions: Some or all CO groups present in
carbonyls can be replaced by monodentate ligands such as alkyl or
aryl isocyanide (CNR) PR3, PCl3, Py, CH3OH etc.
Ni(CO)4 + 4CNR Ni(CNR)4 + 4CO
Ni(CO)4 + 4PCl3 Ni(PCl3)4 + 4CO
Fe(CO)5 + 2CNR Fe(CO)3 (CNR)2 + 2CO
141
4. Action of NO: many carbonyls react with nitric oxide (NO) to
form metal carbonyls nitrosyls. For example:
C
Fe(CO)5 + 2NO 95
Fe(CO)2(NO)2 + 3CO
3Fe3(CO)9+4NO
2Fe(CO)2(NO)2+ Fe(CO)5+Fe3(CO)12+6CO
- +
Co2(CO)8 + H2 165 2[Co (CO)4H ]
C , 200atmpressure
Preparation:
i. It is prepared by job's method by passing CO at 50 atm.
pressure and at room temperature into a suspension of chromic
chloride in ether. Which has been treated with phenyl
magnesium bromide at -70oC.
ii. Chromium hexacarbonyl can be prepared by treating a solution
of a chromic salt dissolved in ether with Al(C2H5)3 and carbon
mono-oxide at a high temperature and pressure.
142
iii. It may also be prepared by carbonylating CrCl3 with CO in the
presence of a reducing agent like LiAlH4.
CrCl3 + CO + LiAlH4 175 Cr.(CO)6 + LiCl + AlCl3
C , 200atmpressure
Properties:
1. Chromium hexacarbonyl exists in colourless rhombic crystals
which sublime without decomposition and dissolve in either,
chloroform, CCl4 and benzene.
2. It is attacked by air, bromine, cold aqueous alkali, dilute acids
conc. HCl and Conc.H2SO4. It is however decomposed by
chlorine or by conc. nitric acid.
2- 2-
Cr(CO)6 Na 2 [Cr (CO)10] + 2CO
NaBH / Liq. NH
4 3
143
2. Both may also be prepared by the action of CO at 225 o and 200
atm. pressure on metallic molybdenum or tungsten reduced in
the presence of copper or iron.
Properties:
1. They are colourless, Mo(CO)6 sublimes at 40oC and boils at
156.4o, whereas W(CO)6 sublimes at 50oC and boils at 175oC.
2. They are stable in air and dissolve in organic solvents like ether,
chloroform, CCl4 and benzene.
3. Mo(CO)6 do not react with air, cold aqueous alkali, acids,
except conc. nitric acid or with thiols or nitric oxide.
4. Bromine and chlorine can decompose Mo(CO)6 and W(CO)6.
5. With pyridine, phenanthroline and ethylene diamine, the CO
group in Mo(CO)6 and W(CO)6 is replaced.
M(CO)5Pyr2 M2(CO)7PYr5 M(CO)3PYr3
M(CO)6 Pyridine
+ 2MgI2
2. By carbonylating MnCl2 with CO in presence of (C8H5)2CONa
2MnCl2+10CO+4(C8H5)2CONa 165 Mn2(CO)10+
C140atm.
4(C6H5)2CO+4NaCl
144
Properties:
1. Manganese carbonyl forms volatile, golden yellow, crystalline,
solid which melts at 155oC in a sealed tube. It is soluble in
organic solvents. It is slowly oxidised in air, especially in
solution.
145
Preparation:
i. It can be prepared by the action of CO on iron powder at 200 oC
and 200 atm. pressures.
Fe + 5CO Fe (CO)5
ii. Recently it has been prepared by the action of CO on Ferrous
iodide in the pressure of Cu which acts as a halogen acceptor.
200C
FeI2 + 4CO Fe (CO)5I2
Properties:
i. Fe(CO)5 is a yellow liquid which is soluble in methyl alcohol,
ether, acetone and C6H6. It is insoluble in H2O.
ii. Decomposition: M thermal decomposition at 250oC it yields
pure Fe.
250C
2Fe(CO)5 Fe + 5 Co
146
vii. Reaction with halogen:
Fe(CO)5 + X2 Fe (CO)4X2 + CO
The velocities of these reactions have been found to follow the
order CI < Br < I.
Preparation
It can be prepared by heating Fe2(CO)9 dissolved in toluene at 70oC.
3Fe2(CO)9 3Fe(CO)5 + Fe3(CO)12
147
Properties
i. Fe3(CO)12 forms deep crystals which are soluble in organic
solvents like toluene, alcohol, ether and pyridine.
B. Carbonyls of Cobalt
It forms two carbonyls
i. Cobalt Octacarbonyl, CO2(CO)8
Preparation
i. It is prepared by the action of CO and the reduced metallic
cobalt at 220oC and 250 atm.
2Co + 8CO Co2(Co)8
ii. When a solution of cobalt carbonyl hydride is treated by an
acid, hydrogen is evolved and Co2(CO)8 remains
2Co(CO)4H Co2(CO)8 + H2
Properties
1. Cobalt octacarbonyl forms orange transparent crystals.
2. It is insoluble in water but is soluble to some extent in alcohol,
ether, CS, etc.
148
3. Action of air: On exposure to air, dicobalt octacarbonyl is
converted into deep violet basic carbonate of cobalt.
6. Dispropotination Reaction
a. Strong bases cause disproportination into Co(+2) and Co(-1)
2Co(CO)8 + 12NH3 2[Co(NH3)6][Co(CO)4]2 + 8CO
Properties:
i. It is black crystalline solid.
ii. It is very unstable easily oxidized by air and can be
recrystallized from hot benzene.
149
C. Carbonyls Of Nickel.
(i) Nickel Tetracarbonyl, Ni(CO)4
Preparation
i. Ni(CO)4 can be prepared by the action of CO on reduced nickel
at 30-50oC.
Ni + 4CO Ni(CO)4
Properties
i. It is colourless liquid, m.p. = -23oC, b.p. = 43oC
ii. It has no solubility in water but dissolved in organic solvents.
iii. It decomposes at 180o-200oC in to nickel and CO.
Ni(CO)4 180 C
Ni + 4CO
3
D. Carbonyls of Ruthenium
It forms three carbonyls :
150
Properties
i. It is colourless soluble liquid having m.p. = -22oC
ii. It has no solubility in water but is soluble in alcohol,
benzene and CHCl3.
iii. It undergoes decomposition to give Ru2(CO)9 and
Ru3(CO)12.
iv. It reacts with halogen to yield Ru(CO)Br and CO.
v. It is photosensitive and yields ruthenium enneacarbonyl.
b. Ruthenium Enneacarbonyl, Ru2(CO)9
It is prepared by exposing pentacarbonyl to u.v. radiation. It
forms yellow monoclinic crystals. It is volatile; it is less stable
towards heat, with iodine. It yield, Ru (CO)2I2.
c. Ru3(CO)12
It is prepared in small quantities along with Ru2(CO)9 when
Ru(CO)5 is heated at 50oC or by exposing Ru(CO)5 to u.v. light.
It is a green crystalline solid.
E. Carbonyl Of Osmium
It forms two carbonyls:
a. Osmium pentacarbonyl. Os2(CO)5
It is a colourless having m.p.-15oC. It is obtained.
i. by the action of CO on OsI3 at 120oC and 200 atm. pressure
in the presence of copper.
ii. by the action of CO on OsO4 at 100oC and 50 atm. pressure.
OsO4 + 9CO Os(CO)5 + 4CO2
b. Osmium eneacarbonyl, Os2(CO)9
It is a yellow crystalline solid. It is prepared by the reaction
of OsI3 with CO in the presence of copper, it is more stable
towards heat than Ru4(CO)9. It melts at 224oC and sublimes
without decomposition.
151
F. Carbonyl Of Iridium
It forms 2 carbonyls:
G. Carbonyl of Platinum
Preparation
i. When CO is passed over PtCl2 at 250oC, PtCl2(CO) and
2PtCl23CO are obtained on heating these yield PtCl2(CO)2.
3PtCl2 + 5CO PtCl2.2CO + 2PtCl2.3C0
Properties
These carbonyls are decomposed by water and HCl.
PtCl2.CO + H2O Pt + 2HCl + CO2
PtCl2.CO + H2O Pt + 2HCl + CO2 + CO
PtCl2.CO + HCl H[PtCl3.CO]
PtCl2.CO + HCl H[PtCl3.CO] + CO
152
(MC O, Thus (MC O) types of bonds were assumed to be
present in metal carbonyls. In the formation of MC O bonds,
the electrons are supplied by the molecules of CO and the metal
atom is thus said to have zero-valency. The Number of molecules
of carbon mono-oxide which can unite with one atom of the metal
is controlled by the tendency of the metal atom to acquire the
E.A.N. of the next inert gas. For the stable nonnumeric carbonyl.
E.A.N. = m + 2y = G
Where M = Atomic number of the metal M
Y = No. of CO molecules
G = At. No. of next inert gas
Carbonyls Atomic Number of electron E.A.N. Succeeding
Number of contributed by CO inert gas
the metal groups
Cr(CO)6 24 12 36 Kr(36)
Fe(CO)5 26 10 36 Kr(36)
Ni(CO)4 28 8 36 Kr(36)
Mo(CO)6 42 12 54 Xe(54)
Ru(CO)5 44 10 54 Xe(54)
W(CO)6 74 12 86 Rn(86)
Os(CO)5 76 10 86 Rn(86)
153
Therefore the metals with odd atomic number cannot form
monocular carbonyls but forms polynuclear carbonyls for example,
Mn(25) and Co(27) form polynuclear carbonyls.
2. Polynuclear Carbonyls:
Sidgwick and Bailey gave the general formula for
polynuclear carbonyls.
X m 2y
G X 1
X
Where G = The At. No. of next Inert Gas.
M = The At. No. of metal atom.
Y = The No. of CO molecules in one
molecule of the carbonyl.
Mn2(CO)10, CO2(CO)8 etc. obey the E.A.N. rule, their E.A.N. per
atom of metal is 36.
For example: E.A.N. of Mn2(CO)10 may be calculated as:
Electrons from 2Mn Atom = 25 x 2 = 50
Electron from 10CO molecules = 10 x 2 = 20
Electrons from one Mn-Mn Bond= 1x2=2
Total = 72
E.A.N. for one Mn atom = 72/2 = 36
The formation of binuclear carbonyls having metal atoms
with odd atomic number can also be explained on the basis of 18-
electron rule as shown below for Co2(CO)8.
Co2(CO)8
2Co = 2 x 9e- = 18e-
8Co = 2 x 8e- = 16e-
Co-Co bond = 1x 2e- = 2e-
Co2(CO)8 = 36e
Electrons on one Co atom = 18e-
154
Drawback
X-Ray diffraction method shows that the bonds are
intermediate between the M-C = 0 and M=C=0 states, i.e. there is
some double bond character in M-CO. The EAN rule does not explain
double bond character. This is explained by both MOT and VBT.
155
is expected that there is some additional bonding mechanism in the
formation of metal-carbon monooxide bonds in the metal
carbonyls.
Mechanism
1. Firstly, there is a dative overlapping of filled carbon -orbital
i.e. 2sp hybrid orbital with an empty metal -orbital (MCO)
as in the figure 5.1.
- m + + C = 0 : - M + C = O:
156
Fig. 5.2(b) M - CO and π bonding
157
3. Raman Spectra shows that nickel atom in the nicle carbonyl
must be tetrahedrally hybridised as in the figure 5.3.
Evidences:
1. The above structure (Fig. 5.3) is supported by the following
reactions:
i. When an alcoholic solution of the carbonyl is treated with
orthophenanthroline to yield a stable ruby-red compound
Ni(CO)2 phen. It confirms that two C=O groups of Ni(CO) 4
are replaced by one molecule of phenanthroline.
ii. Similarly the reactions of Ni(CO)4 with diarsine indicates the
two C=O groups are replaced and remaining two are retained.
158
2. Structure of Fe(CO)5: The various evidences are:
i. The vapour density and the freezing points of benzene
solution shows that its molecular formula is Fe(CO)5.
ii. Electron diffraction, Raman and I.R. spectra shows that it has
trigonal bipyramidal shape and Fe-C axial bond and Fe-C
basal bond lengths are equal to 1.797Ao and 1.842Ao
respectively. It has dsp3 hybridisation of Fe atom (Fig. 5.4(c).
Structure of Cr(CO)6
It has octahedral configuration. The internuclear bond
lengths are:
Cr-C Cr-O C-O
1.92 3.08 1.16Ao
According to old concept when chromium forms Cr(CO)6
one electron of 4s orbital missing and three 4p orbitals become
empty which are hybridised to form six d 2sp3-hybrid orbitals six
molecules of CO donate a lone pair of electrons each to six vacant
hybrid orbitals to form six CrCO -bonds as shown in the Figure
5.5. Therefore Cr(CO)6 molecule is diamagnetic in nature and
octahedral in geometry.
159
When chromium atoms form chromium carbonyl [Cr(CO)6]
the metal atom exhibits d2sp3 hybridisation. Out of 6 d2sp3 hybrids
three hybrid orbitals are half filled and three hybrid orbitals are
empty. Three electrons remain in 3d orbitals as shown in the figure.
5.5(a) and (b). The Bond Structure of Cr(CO)6 Shows 2 kinds of
bonds between Cr and Co.
(a) Simple Covalent Bonds Cr-C 0 (b) Double bonds Cr c=O
In the resultant resonance structure all Cr-C bonds have been
identical, each of the 6 CO groups get linked to the metal atom by a
bond are constructed from the d-orbitals of the metal atom. CO
(groups I) are bound to the metal atoms by simple ionic bonds.
160
Thus, the bond structure of Cr(CO)6 shows 2 kinds of bonds
between Cr and CO.
i. Simple covalent bonds Cr-C 0 (I)
ii. Double bond Cr = 0 (II)
161
Fig. 5.6
162
The co-ordination number of each Fe atom is not equal to 6
but equal to 7.
163
Fe3(CO)12 each of the two Fe atoms is linked with three terminal CO
groups, two bridging CO groups and third Fe atom is linked with four
terminal CO groups and to each of two Fe atoms.(Fig. 5.9 (b). It is
also shown by a structure similar to Fig. 5.9.
Structure of Fe3(CO)12
According to old concept each iron atoms gets hybridized
trigonal bipyramidally (dsp3). The three trigonal bipyramides get
arranged in such a manner so that the carbonyl groups at two of the
equatorial apices of each bipyramid and held in common by two
bipyramides dxz and dyz orbitals are available to form Fe-Fe bonds. It
is solid. The three Fe atom get situated at the corner of an isosceles
triangle and the twelve CO arranged at the twelve CO arranged at the
vertices of an icosahedra. Two Fe-Fe bond lengths are 2.698 Ao and
one Fe-Fe bond length is 2.56Ao. (Fig. 5.9)
164
Fig. 5.9 (b) Structure of Fe3 (CO)12
(c) Tetra and Hexanuclear Carbonyls
On the similar grounds structures of tetranuclear carbonyls, such as
M4(CO)12 [M = Co, Rh, Ir] and hexanuclear carbonyls, M6(CO)16 eg.
Rh6(CO)16 can be represented as in Figs. 5.10 and 5.11 respectively.
Some heteronuclear carbonyls are also known e.g. Mn2Fe(CO)14 is
shown in Fig. 5.12.
(a)
(b)
Fig. 5.10 (a) Structure of Ir4(CO)12
(b) M4(CO)12; M = Co or Rh
165
Fig. 5.11 Structure of Rh6(CO)16
166
quantitative interpretation impossible. That the extent of bonding to
terminal and bridging carbonyls is different is clearly shown by carbonyl
stretching frequencies. Carbon monoxide itself has stretching frequency
of 2143 cm-1; neutral metal carbonyls known to have no bridging
carbonyl groups have stretching frequencies in the range 2125-2000 cm-1;
and Fe2(CO)9 and Co2(CO)8, in addition to showing bands in this region,
also show carbonyl absorption at 1830 and 1860 cm-1 respectively. In
general, carbonyl absorption in the 1900-1800 cm-1 region is indicative of
the presence of bridging carbonyl groups in uncharged species, though
the presence of other groups may result in the lowering of the stretching
frequencies of terminal carbonyl groups into this region (in carbonylate
anions such as [Co(CO)4]- and [Fe(CO)4]2- very low carbonyl stretching
frequencies of 1883 and 1788 cm-1 respectively result from the strong
metal-carbon bonding which stabilizes the low oxidation state of the
metal. In a few neutral species believed to contain carbonyl groups
bonded to three metal atoms, stretching frequencies of 1800 cm-1 or less
are found.
Thus, in summary the terminal carbonyl absorption is obtained in
the range of 2125-2000 cm-1, while bridging carbonyl frequency is
obtained in the 1900-1800 cm-1 region. While, the strong metal carbon
bonding is indicated by very low carbonyl structing frequencies of 1883
and 1788 cm-1 respectively.
167
Check Your Progress-1
Notes :(i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of the
unit.
(a) Generally metal carbonls involve............................... -and .........
..................... -bonding between CO and metal atom.
(b) Metal atoms with even number of electrons easily
form............carbonyl, but the metal ions with odd number of
electrons give.......................or...............................
(c) I.R. spectra of carbonyls show C-O stretching frequency
at..........................cm-1 for the terminal carbonyl group and
at................cm-1 for the bridging carbonyl group. The M-CO π
bond is indicated by the absorption at...................and.............Cm-1
respectively.
(d) While Mn2(CO)10 has........................bridging carbonyl group,
Fe2(CO)9 has................................................................................
168
ii. A negative ion NO- is formed due to the gain of an electron from
some electropositive metal and it has structure as below:
(:N:: O)- or (:N=O:)-
Mode (I) is rarely seen, while (II), (III) and (IV) modes are formed
after transferring one electron to the metal atom. Out of these modes (II)
and (III) are similar to the carbonyl group linked with a metal atom.
Mode (V) is seen only in a few complexes only, e.g. [Co(CN)5NO].
169
NO replaces neutral CO, hence it is supposed to be a complex of neutral
NO. However, the experimental evidences are not supportive.
170
stretching frequency in complexes of NO+ is some 300-500 cm-1 lower
than that in salts such as NO+BF4-.
171
5.3.4 Nitrosyl Carbonyl Complexes
Mononuclear nitrosyl carbonyls are restricted to the following
compounds; Co(NO)(CO)3, Fe(NO)2(CO)2, Mn(NO)3CO and Co(NO)3
(isoelectronic with Ni(CO)4; Mn(NO)(CO)4 (isoelectronic with Fe(CO)3;
and V(NO)(CO)5 (isoelectronic with Cr(CO)6). In addition a binuclear
species Mn2(NO)2(CO)7 (isoelectronic with Fe2(CO)9 and a number of
nitrosyl complexes containing organic groups or triphenylphophine as
substituents have been prepared. Nitric oxide displaces carbon monoxide
from V(CO)6, (Ph3P)2Mn2(CO)8, Fe2(CO)9 and Co2(CO)8 to give
V(NO)(CO)5, Mn(NO)(CO)4, Fe(NO)2(CO)2 and Co(No)(CO)3
respectively; the further action of nitric oxide on the manganese and
cobalt compounds yields Mn(NO)3(CO) and Co(NO)3. All of these
substances are solids of low melting point or liquids which are thermally
rather unstable and are decomposed by air and by water. In the reaction of
Fe(NO)2(CO)2 with alkali in methanol, [Fe(NO)(CO)3]- is formed, but
under comparable conditions Co(NO)(CO)3 gives [Co)CO)4]-, Co(OH)2
and other cobalt-free products.
The limited evidence available is consistent with tetrahedral
structures for Fe(NO)2(CO)2 (Fig. 5.14) and Co(NO)(CO)3 and a trigonal
bipyamidal structure (with NO in the equatorial plane) for Mn(NO)(CO)4
(Fig. 5.15); (Ph3P)2Mn(NO)(CO)2 also has a trigonal bipyramidal
structure, the two triphenylphosphine molecules occupying the apical
positions. Since Co(NO)3 shows two N-O stretching frequencies in the
infrared, it must be pyramidal rather than planar, but the detailed structure
is not known.
172
presence of finely divided iron as a halogen-acceptor. These readily lose
NO to give [Fe(NO)2X]2, in which the halogen atoms act as bridges.
Analogous compounds of cobalt and nickel may be formed by reactions
similar to those involved in the high pressure synthesis of carbonyls; for
example,
CoX2 + Co + 4NO 2Co(NO)2X
4NiI2 + 2Zn + 8NO 2[Ni(NO)I]4 + 2ZnI2
20
M(CO)6 + 2NOCl M(NO)2Cl2 + 6CO
CH 2 Cl 2
173
In the latter process, two successive equilibria are involved:
174
+ NO+ + 3CO Co(NO)(CO)3 In this compound the E.A.N. of Co
is, 27+1+2+6 = 36 of stable Krypton.
M + NO M- + NO+ M2- - N+ = 0+
N
π
O: N – O -N
π
O+:
M--N
π
O: M- N
π
O M
π
N
π
O: M--N-O
Nitric oxide is a paramagnetic molecule with an electron in
175
an anti-bonding orbital. This electron is relatively easily lost with
formation of the NO+ ion and an increase in the N-O stretching
frequency from 1878 cm-1 in NO to 2200-2400 cm-1 in nitrosonium
salts.
Structure of various groups of nitrosyl complexes are shown
in Fig. 5.13 to 5.20
176
Fig. 5.16: Structure of [Fe(NO)2I]2
177
Fig. 5.19: Red salt of Diethyl Ester of [FeS2(NO)4]2-
178
Many other complexes containing one or two (but not, so far,
more) molecules of coordinated nitrogen have now been prepared, and it
is clear that N2 acts as a -donor and π-acceptor in the same way as
isoelectromic CO, though the complexes formed are much less stable
than carbonyls. Much of the interest in this field centres on the possibility
of developing new methods for nitrogen fixation; up to the present time,
however, no method has been found for the reduction of nitrogen in the
complexes described here (though this has been achieved by systems
involving an organ titanium complex under powerfully reducing
conditions).
NaBH 4
CoCl2 + Ph3P (Ph3P)3CoH3
N
(Ph3P)3CoH(N2)
3
EtOH
[Ru(NH3)5H2O]2+
N
[Ru(NH3)5(N2)]2+
3
MeSO3 H
[Ru(NH3)5Cl]2+ N3- [Ru(NH3)5N2]2+
NH 3
179
(d) Reaction of coordinated NH3 with HNO2:
180
Fig. 5.21: Structure of [Ru(NH3)5(N2)Ru(NH3)5]
181
The active enzyme in fixation nitrogen is nitrogenase. In this
enzyme two proteins take part in the reaction. Small protein has
molecular weight of 57000-73000 and contains Fe4S4 group; while the
large protein is a tetramer of molecular weight 220000-240000. It has 2
molybdenum atoms, nearly 30 iron atoms and nearly 30 mobile sulphide
ions. Fe-S group probably functions as redox centre, and the active site
for dinitrogen binding is probably molybdenum atom. (Fig. 5.23)
Amongst all the donor atoms oxygen is most important. The donor
ability of oxygen is related with its partial charge; higher is the negative
charge, higher will be the donar ability. Large number of coordination
compounds are available in which oxygen uses one of its two lone pairs
of electrons.
The most important example of dioxygen complexation is
transportation of oxygen in aerobic-organisms through heme and
hemocynin mechanism. Although, hemoglobin and hemocynin are known
since long time for their specific ability of absorption and release of
182
oxygen; but now a number of synthetic compounds have this property,
e.g. Bis (Salicylic) ethylenedimmine cobalt (II).
5.5.2 Hemoglobin
Hemoglobin is the red pigment of blood. It has two parts: (a) 96%
part of it is a simple, specific protein called globin and (b) 4% remaining
part is the prosthetic group hence:
Globin
Hemoglobin
Heme Protoporphyrin
Fe(II)
183
It is a globular protein, which is made up of polypeptide chins.
These chains are arranged in a regular tetrahedral form and are linked
with the four rings of pyrole. Molecular weight of hemoglobin is nearly
64500.
Hemoglobin molecule can coordinate with dioxygen without
oxidation of iron. The bonding of iron with dioxygen is so strong that
oxyhemoglobin does not decompose during its transportation in the body.
Still it is so weak that its contact with oxidase decomposes it readily. The
various steps during oxidation of hemoglobin are:
IInd step: Bonded dioxygen links with other heme ( -peroxo complex
is formed) :
184
steps III and IV are checked by sterric hinderance. Thus dioxygen is
carried away by oxyhemoglobin and either stored in oxymyoglobin or
given to cytochromes for use.
185
triphenylphosphine in a variety of organic solvents, the solvent serving as
the source of the carbonyl group:
(NH4)2IrCl6 (Ph3P)2Ir(CO)CI
Ph P 3
Fig. 5.24
186
Check Your Progress-2
187
5.7 LET US SUM UP
188
(a) (b) (c) (d)
D D
:N :N :N :N
:O: :O: :O: :O:
Links with Links with Links with Links with
bonds and bonds dative bonds dative bonds
(neutral) (cationic) (cationic) (cationic)
Pure nitrosyls have general formula M(NO)4 with M = Fe, CO, Ru.
However Co(NO)3 has also been reported.
189
a redox centre and the active site for dinitrogen binding is
molybdenum atom.
Amongst all the donar atoms oxygen is most important. This ability
is related with its partial charge.
The most important example of dioxygen complexation is
transportation of oxygen in aerobic organisms, through heme and
hemocynin mechanism.
190
5.8 CHECK YOUR PROGRESS: THE KEY
191
Unit - 6 REACTION MECHANISM OF TRANSITION METAL
COMPLEXES-I
Structure
6.0 Introduction.
6.1 Objectives.
192
6.0 INTRODUCTION
However, you may recall what you have already studied about the
basic concept of kinetics and of current views on the nature of
193
substitution at a saturated carbon atom, as inevitably organic chemical
thinking has expected a great influence on the interpretation of the
kinetics of inorganic reactions.
6.1 OBJECTIVES
The main aim of this unit is to look in detail at the evidence and
experiments that are used in the analysis of reaction pathways and
develop a deeper understanding of the mechanism of substitution
reactions of d-block metal complexes. After going through this unit you
should be able to:
discuss the energy profile of a reaction and explain lability in
terms of VBT and CFT principles;
describe nuelcophilic substitution reactions in octahedral
complexes in terms of SN1 and SN2 reaction mechanisms, and the
evidences supporting them;
explain acid- and base-hydrolysis reactions and their mechanisms;
explain water exchange (Anation) is a binuclear reaction and the
rate of this reaction depends upon the nature of the metal ion; and
describe the catalysts form octahedral substitution reactions;
194
the form of the products. Unless this takes place using a suitable
mechanism, the reaction will not take place. On the thermodynamic basis,
the possibility of conversion of reactants, into products is only when the
state of disorder and the bond-energies in the products are relatively high.
Both of these, affect the direction of a chemical change and on the effect
of these depends the important thermodynamic functions Gibb's free
energy, G. For a chemical reaction, free energy is related with the heat
content or the useful energy, H , and the disorder, S , according to the
following relation:
G = H - T S
195
ligands is called the lability of the complex. The complexes that undergo
rapid substitution (half time period or T1/2 or reaction rate k is used to
denote the speed of the reactions) are termed labile, whereas those with
low rates of substitution are called inert.
196
because, the use of outer d-orbitals does not make effective overlap
between metal and ligand orbitals resulting in weaker bonds.
Fig. 6.1
197
Table 6.1 Distribution of dn-electrons in various t2g orbitals for
labile and inert inner-orbital octahedral complexes
(according to VBT)
n
Type of the d Distribution of dn electron (shown by Example of central
complex configu arrows) in t2g orbitals. Electrons shown by metal ions
ration crosses in eg orbitals have been donated by
six ligands to enter d2sp3 hybrids and are
in opposite spins.
d s p
t2g eg
xy yz zx x -y z2 2 2
px py pz
0
inner d xx xx xx xx xx xx Sc(+3), Y(+3), rare
orbital earth (+3), Te(+4),
labile
Zr(+4), Hf(+4), Ce(+4),
octahedral
complexes Th(+4), Nb(+5), Ta(+5),
Mo(+6), W(+6)
d1 xx xx xx xx xx xx Ti(+3), V(+4), Mo (+5),
W Re(+6)
d2 xx xx xx xx xx xx Ti(+2), V(+3), Nb (+3),
Ta(+3), W(+4), Re(+5),
Ru(+6)
inner d3 xx xx xx xx xx xx V(+2), Cr(+3), Mo(+3),
orbital W(+3), Mn(+4), Re(+4)
inert
octahedral
complexes
d4 xx xx xx xx xx xx [Cr(CN)6]4-, Mn(CN)6]1
Re(+3), Os(+3), Ir(+4)
4-
d5 xx xx xx xx xx xx [Mn(CN)6] , Re(+2),
Fe(CN)6]3- Ru(+3),
Os(+3), Ir(+4)
4-
d6 xx xx xx xx xx xx [Fe(CN)6] , Ru(+2),
Os(+2), Co(+3)
(except Co Fe34-
Rh (+3), Ir (+3)
198
Table 6.2 Loss in CFSE, E (in the units of Dq) in the formation of
a pentagonal bipyramidal intermediate in octahedral substitution reactions
on the basis of SN2 associated mechanism
Table 6.3 Loss in CFSE, E (in the units of Dq) in the formation of a
pentagonal bipyramidal intermediate in octahedral substitution reactions
on the basis of SN1 associated mechanism
199
SN1 association mechanism
Octahedral (oct.) Syware Pyramidal (Squ. pyi)
(C.N. = 6) (C.N. = 5)
dn ion Strong ligand field (spin-paired Weak ligand field (spin-paired
or low-spin complexes) or low-spin complexes)
Oct. pent.bipy. E Oct. pent.bipy. E
(C.N.= 6) (C.N.=5) (C.N.= 6) (C.N.= 5)
d0 0 Dq 0 Dq 0 Dq 0 Dq 0 Dq 0 Dq
d1 4 4.57 0 4 4.57 0
d2 8 9.14 0 8 9.14 0
d3 12 10.00 -2-00 12 10.00 -2
d4 16 14.57 -1.43 6 9.14 0
d5 20 19.14 -0.86 0 00 0
d6 24 20.00 -4.00 4 4.57 0
d7 18 19.14 0 8 19.14 0
d8 12 10.00 -2.00 12 10.00 -2
d9 6 9.14 0 6 9.14 0
d10 0 0.00 0 0 0.00 0
The value of CFSE mentioned are in the units of Dq and have been
given for both the fields viz. strong field and weak field and for both the
mechanism (SN1, and SN2).
200
The octahedral complexes formed by the ions for which there is
large loss in CFSE are least labile i.e. such complexes are inert.
The ion with maximum loss of CFSE will form the most inert
complex. Thus the order of inertness of low spin complexes formed by d 3,
d4, d5 and d6 ions is:
The order of reactivity will be reverse of the above i.e. the order of
reactivity will be d6 > d3> d4 > d5 it is supported by the following facts:
i. High spin octahedral complexes of d3 ion will react slowly, i.e. these
are inert complexes because for this ion there is substantial loss in
CFSE whether the substitution mechanism is SN1 or SN2.
201
ii. High spin octahedral complexes of d5 ion react rapidly i.e. these are
labile complexes, since there is no loss in CFSE.
iii. Both high spin and low spin octahedral complexes of d8 ion are inert.
202
3. Charge to Radius Ratio Values: Octahedral complexes having
the central metal ion with the largest charges to radius ratio will
react slowest (Fig. 6.2).
i. The first row transition elements [Ni(H2O)6]2+ (a d8 system)
has the largest value of half life i.e. it reacts slowest. The
hydrated M2+ ions [M(H2O)x]2+ of the first row transition
elements are all high spin complexes.
ii. [Cu(H2O)6]2+ reacts most rapidly because the 2 water
molecules above and below the square plane of the tetragonal
distorted octahedral shape of [Cu(H2O)6]2+ are exchanged. The
remaining four H2O molecules lying in the square plane react
slowly.
203
while 6-co-ordinated complexes like [Mn(CN)6]4- and [Co(CN)6]3-
have the same stability as [Ni(CN)4]2+. The greater reactivity of
4-co-ordinated complexes may be due to the fact there is enough
room round the central ion for the entry of a 5 th group into the co-
ordination sphere to form on activated complex.
204
6.3 KINETICS OF OCTAHEDRAL SUBSTITUTION
[LnM] + y
[LnMY] + X
fast
205
first order with respect to MX5Y and first order with respect to Z.
Thus
for SN1 mechanism rate = K [MX5Y],
and
for SN2 mechanism rate = K [MX5Y][Z]
Here, it may be mentioned that the kinetic data would be
equally compatible with ion-pair formation (if both reactants are
ions) followed by a unimolecular reaction of the ion-pair:
[Ln MX] + Y
k1
[Ln MX] Y
[Ln MX] y [Ln MY] + X
slow
This leads to
d k k [ L MX ][Y ]
[Ln MY] = 1 2 n
dt k 1 k 2
= k[Ln MX][Y]
where
k1k 2
k=
k 1 k 2
206
whether the rate determining steps is the formation of a new Y...............M
bond or the dissociation of an old M...................X bond.
207
(3) Increase in the electron density on Co atom by the electron
donors in SNn should assist the M-L bond breaking.
(4) k1 is independent of the nature of E as well as its concentration
except for the OH- group for which the reaction is of the second
order.
(5) Cis effect. Ligands having another pair of electrons like CNS - or
OH- increase the rate of hydrolysis of the complexes about ten
fold when present cis to L, as compared to the rate when they are
present trans to L. This is due to the stabilization of the square
pyramidal complex by the electron pair donation by OH- or CNS-
along the Cis position through p-d- bonding (Fig. 6.4). No
rearrangement takes place and the product is 100 percent Cis
isomer. The ligands that do not show the eis effects are those that
do not have an extra pair of electrons (NH3) or are themselves
acceptors (NO2-, CO, NO, etc.).
From Table 6.4, it can be seen that for the formation of the
5-coordinate intermediate, high energy changes are required for
the low spin d3, d6 and d8 and high spin d3 and d8 ions. Hence,
these complexes do not favour the SN1 mechanism for the
substitution.
208
System High spin Low spin
CN = 5 CN = 7 CN = 5 CN = 7
do, d10 0.00 0.00 0.00 0.00
d1 0.57 1.28 0.57 1.28
d2 1.14 2.56 1.14 2.56
d3 -2.00 -4.26 -2.00 -4.26
d4 3.14 -1.07 -1.43 -2.98
d5 0 0 -0.86 -1.70
d6 0.57 1.28 -4.00 -3.52
d7 1.14 2.56 1.14 -5.34
d8 -2.00 -4.26 -2.00 -4.26
d9 3.14 -1.07 3.14 -1.07
209
with respect to the complex, MX5Y and first order with respect to the
entering ligand, Z, i.e.,
Rate of reaction = K[MX5Y][Z]
In the second step either at the same as Z adds to MX5Y or
shortly thereafter, Y leaves MX5YZ rapidly to give MX5Z. This is a
fast step.
MX5YZ Fast
MX5Z
Unstable seven- -Y (C.N.=6)
coordinatee Intermediate
(C.N.=7)
Both these steps are shown diagrammatically in Fig. 6.1
This mechanism is similar to Eigen-Wilkins Mechanism,
which presents formation of the association complex [L-MX5-Z] in
the pre-equilibrium step: Thus the following equilibrium will be
established:
[ LMX 5 .Z ]
LMX5 + Z MX5. Z; K =
[ LMX 5 ][ Z ]
210
Hence, if the t2g orbitals are filled (Co2+ in low spin
octahedral complexes), the higher activation energy required to
empty one of the t2g orbitals will make the complex inert.
Table 6.4 also shows that due to the loss of the CFSE
energies, the d3 and low spine d6 ions require highest activation
energies, followed by d7, d8 (Ni2+complexes are labile due to the
expulsion of ligand by the eg orbitals) and high spin d3 and d8 ions.
(ii) The rate of SN1 mechanism is first order with respect to MX5Y,
i.e., the rate-determining step in this mechanism is unimolecular.
On the other hand the rate-determining step for SN2 mechanism is
bimolecular, i.e. its rate of reaction is second order: first order
with respect to MX5Y and first order with respect to Z. Thus:
for SN1 mechanism rate = K[MX5Y]
and for SN2 mechanism rate = K[MX5Y][Z]
211
while (b) the reactions, in which a hydroxo complex is formed by the
replacement of a ligand by OH- group are called base hydrolysis reactions.
Acid hydrolysis reactions occur in neutral and acidic solutions
(pH<3) while base hydrolysis reactions occur in basic solution (pH 10).
Examples are:-
[CoIII(NH3)5Cl]2+ + H2O[CoIII(NH3)5(H2O)]3+ + Cl- Acid hydrolysis
[CoIII(en)2ACl]+ + H2O [CoIII(en)2A(H2O)]2+ + Cl- reaction
[A = OH-, Cl-, NC-, NO2-]
212
The rate law for acid hydrolysis at low pH thus becomes
d
- [Co(NH3)5X] = kA[Co(NH3)5X]
dt
(If X is the anion of a weak acid, a term
kH+[Co(NH3)5X][H+] is added.) As we have shown previously, such
a rate law is compatible with either a slow dissociation of the
complex into [Co(NH3)5]3+ and X or replacement of X by H2O as the
rate-determining step. In order to try to decides between these
alternatives, the rates of hydrolysis of a series of complexes of
formula [Co(AA)2Cl2]+, where AA is a substituted ethylendiamine,
were examined. For replacement of a single chloride ion at pH 1 the
order found for values of kA was
213
(b) the decrease in the rate of the exchange reaction
[Co(NH3)5(H2O)]3+ H218O = [Co(NH3)5(H218O)]3+ + H2O at high
pressures.
214
The replacement of NH3 molecules by polyamines increases the
size of the complex i.e. the chelated complex has larger size. The larger
the size of the ion less its solvation energy will be and hence less easily it
will be formed. Thus the stability of the transition state in which the Cl
ion is only partially lost and in which the solvation is less efficient will be
reduced. The rate of equation is slowed down by chelation because of
reduced stability of the transition state due to less efficient solvation.
215
1. SN-2, Displacement Mechanism
The reaction proceeds as:
( OH )
[Co(NH3)5Cl]2+ slow
+
[Co(NH3)5(OH)Cl]
2+
[Co(NH3)5(OH)] + Cl
fast -
[(NH3)4Co(NH2)Cl]+ slow
2+
[(NH3)4Co(NH2)] + Cl
-
(6.2)
2+ 2+
[(NH3)4Co(NH2)] +H2O [(NH3)5Co(OH)]
fast
(6.3)
216
The rate determining step is the dissociation of the
amido complex given in Eq.(6.2) whose concentration would
depend upon the concentration of hydroxyl ions present. This
is the SN1CB process.
The rate law will be-
d K1K 2[Co ( NH 3 )5 Cl ][OH ]
= [Co(NH3)5OH] =
dt K 1[ H 2O] 2 K 2[ H 2O]
= K[Co(NH3)5Cl][OH]
K1 K 2
where, K=
K 1[ H 2O]2 K 2 [ H 2O]
217
Direct and Indirect Evidences in Favour of Conjugate Mechanism:
Equation 6.1 requires that the reacting complex should have at
least one Photonic hydrogen atom (H+) on a non-leaving ligand so that H+
may transfer to OH- to form its conjugate acid H2O and conjugate base,
[Co(NH3)4(NH2)Cl]+ of [Co(NH3)5Cl]2+ which acts as an acid. Thus a
complex having no proton should react with OH- much more slowly and
the rate of reaction would be independent of the concentration of OH -. It
is observed that the complexes like [Co(Cn)2Br] and trans [Co-(Py)4Cl2]+
which does not have N-H hydrogen undergo hydrolysis much more
slowly in basic solution at a rate which is independent of [OH-] over a
wide range. Thus in the absence of an acidic portion on the ligands an
SN1 CB mechanism is not possible.
Thus both the mechanisms give the same rate laws and the same
hydroxo products in aqueous solution, because water is a good co-
coordinating agent. The rate of formation of [Co(en)2(NO2)Y]+ depends
only on the concentration of the base, OH, not on the nature or
concentration of Y-, OH- and piper; dine are used as catalysts while N3-,
NO2-, SCN- ion are used as nucleophiles.
218
Which increase the rate of base hydrolysis reaction and form
peroxo products.
[L5M] + Y
k 1
[L5MY]
Since Y competes with solvent water for the active intermediate
[L5M], the rate of formation of [L5MY] can be dependent on the
concentration of Y. On the other hand, there should be some high
219
concentration of Y at which the rate of replacement of water no longer
depends on the concentration of Y. The rate of formation of [L 5MY] at
this concentration should be equal to the rate of formation of [L5M] and
also equal to the rate of exchange of water between [L5M(H2O)] and the
solvent. Thus the rate of formation of [L5M] is given by
d
[L5M] = k1[L5M(H2O)] - k-1[L5M][H2O] - k2 [L5M][Y]
dt
According to the steady-state approximation, the concentration of
the very reactive [L5M] remains small and constant during the reactions
d
(i.e. [L5M] = 0 at the steady state). Thus,
dt
K1[[L5 M(H 2O]
[L5M] =
K 1[ H 2O] K 2 [Y ]
and
d K K [L M(H 2O][Y ]
[L5MY] = 1 2 5
dt K 1[ H 2O] K 2 [Y ]
220
[Co(NH3)5CO3] and nitrito complex [Co(NH3)5ONO]2+ from hydroxo or
aquo-complex, [Co(NH3)5H2O]3+.
The most likely path for the equation of the carbonato complexes
seems to be the electrophilic attack by the proton on the O atom bonded
to the metal, so that no O is found in the complex when the equation is
carried out in presence of H2O (Fig. 6.6).
221
Check Your Progress-2
Notes : (i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of the unit.
(a) SN-1 and SN-2 mechanism of substitution reactions differ in -
(i) In SN-1 rate determining step is.............................process, while
that in SN-2 is .......................process.
(ii) The rate determining step in SN-1 is...................molecular, while
that in SN-2 is ....................... molecular.
(iii) In SN-1 rate = ......................................
while that in SN-2 rate = ......................................
(b)(i) For acid hydrolysis at low pH, the rate Law is -
...................................=.................................................
(ii) The rate law of base hydrolysis reactions of an octahedral
ammine complex, by SN-1 CB process is -
d
= [Co(NH3)5OH] = .................................
dt
= ...................................
(iii) Formation of aquo-complex from a carbonato complex is an
example of substitution...................... bond, and involves..............
attack on....................
222
On the thermodynamic basis, Gibbs free energy for the reaction
should decrease, in order to the reaction takes place, i.e. G
should be negative.
Since,
G = H - T S, hence the possibility of conversion of reactants
The inner orbital complexes may be labile only when they have at
least one d-orbital in t2g set is vacant; e.g. [V(NH3)6]3+ ion,
223
In SN-1 or dissociation mechanism, the rate determining slow step
is a metal-ligand bond breaking step, since the coordination
number of the complex, MX5Y (=6) is decreased to 5 in the
intermediate, MX5, complexes:
Y Z
[MX5Y] [MX5] [MX5Z]
(C.N.=6) (C.N.=5) (C.N.=6)
224
The rate of acid hydrolysis reaction is of first order -
[Co (NH3)5X]2+ + H2O [Co(NH3)5(H2O)]3+ + X-
[(NH3)5CoCl]2+ + OH- +
[(NH3)4Co(NH2Cl)] + H2O
Fast
[(NH3)4Co(NH2)Cl]+ Slow
2+
[(NH3)4Co(NH2)] + Cl
-
= K [Co(NH3)5Cl][OH-]
The reactions involving removal of coordinated water molecule are
known as 'anation' reactions:
225
This reaction is reverse of acid hydrolysis reaction. The same
second order kinetics would be observed for a unimolecular process:
[Co(NH3)5(H2O)]3+ Slow
[Co(NH3)5]
H 2O
3+ Fast
X
[Co(NH3)5X]2+
(ii) G = H - T S
That is .......................should be very high i.e. H should be
negative and T S should be positive.
226
(b)(i) Rate law is -
d
- [Co(NH3)5X] =KA[Co(NH3)5X]
dt
K1 K 2 [Co(NH3 ) 5 Cl][OH - ]
(ii) =
K 1[ H 2 O] 2 K 2 [ H 2 O]
= K [Co(NH3 )5 Cl][OH- ]
227
M.Sc. (Previous) Chemistry
BLOCK – III
Complexes-II
228
UNIT 7 REACTION MECHANISM OF TRANSITION METAL
COMPLEXES-II
Structure
7.0 Introduction
7.1 Objectives
229
7.0 INTRODUCTION
The factors that influence the rates of electron transfer reaction are
many more. Transfer of electron from one species to other may take outer
sphere root or the inner sphere one. During the first root, bond-formation
and bond cleavage does not take place; while during the later root excited
species are involved. However, the quantitative understanding of the rates
of inorganic reactions is far from secure, and in most cases all that it is
possible to do is to distinguish reasons for differences in the order of
magnitude of rate constants.
7.1 OBJECTIVES
The main aim of this unit is to study the Kinetics and mechanism
of redox reactions. After going through this unit you should be able to :
230
7.2 RE-DOX REACTIONS
231
These reactions occur by direct electron transfer and the electron
effectively hops from one species to the other and the ligands act as
electron-conduction media. It involves movement of an electron from the
outside of a ligand in one co-ordination sphere over the outside of a
second sphere. This mechanism is appropriate with large conjugated
ligands like phenonthroline and bipyridine.
The reaction is fast with second order constant 105 at 25oC and
there is no heat change in the reaction and gives same products after the
electron transfer both the axions are inert.
232
The reaction rates for outer sphere redox reactions, where the
complex retains its full coordination sphere, and the electron must pass
through both the coordination shells (a tunneling mechanism), vary from
(second order rate k2) 10-4 for [Co (C2O4)3]3- - [Co(C2O4)3]4- through 103
for MnO4- – MnO42- to more than 106 for [Fe (dipy)3]3+ - [Fe (dipy)3]2+
and [W(CN)8]3- - [W (CN)8]4- complexes.
Where both reactants are non-labile, e.g. in the case of [Fe (CN)6]4-
and [Fe(CN)6]3-, a close approach of the metal atoms is impossible, and
the electron transfer must take place by a tunnelling or outer sphere
mechanism. Although for an isotopic change the equilibrium constant is
nearly unity and Go is nearly zero, activation energy is required to
overcome the electrostatic repulsion between ions of like charge, to
distort the coordination of both species and to modify the solvent
structure around both species.
233
state such as
A small cation holds its hydration sheath too strongly, whilst a very
large one does not bring the anions into close proximity. It is interesting
to note that the MnO42- - MnO4- exchange reaction is also subject to alkali
metal ion catalysis, the order of effectiveness being the same as for the
[Fe (CN)6]4- - [Fe (CN)6]3- reaction.
O+R [ O .... R ]
[ O .... R ] [ O .... R ]*
[ O .... R ]* [ O- .... R+ ]
[ O- .... R+ ] O - + R+
First the oxidising agent ( O ) and the reducing agent (R) come
closer to form precursor complex. During activation of the precursor
complex there is reorganisation of solvent molecules and the bond lengths
234
of metal ligand bonds are changed. However this takes place before the
electron transfer. In the last step ion – pairs are transformed in to product
ions.
(2) Fast electron transfer takes place when the electrons are able
to reach the surface of the complex through conjugation (in
the ligands attached) or through monatomic ligands.
(4) The rate constant depends upon the cation present in the
solution; ion pair formation decreases the activation energy
by reducing the electrostatic repulsion energy.
235
of energy, it will be more advantageous, the ion – ligand bond – length
stabilize at the intermediate value. At this point electron transfer takes
place at the bond – length of reactants.
236
this reaction, one electron from t2g orbital of Fe (II) is transferred to t2g
orbital of Fe (III). The bond-lengths in Fe (II) and Fe (III) complexes are
different (In octahedral high spin complex of Fe (II) = 92 pm and that of
Fe (III) = 78.5 pm), which indicates the energies of orbitals are not
equivalent. If the electron transfer takes place without losing energy, then
we will get the product in which bond-length of Fe (II), complex is equal
to the characteristics bond – length of Fe (III) – complex and vice versa.
But this will be against the first law of thermodynamics. Actually, it is
necessary to give energy for electron – transfer. The actual reaction starts
with smaller bonds in Fe (II)-b. Complex and larger bonds in Fe (III) –
complex; unless the energy of participating orbitals become equal. The
vibrational stretching and compressions of metal – ligand bond help in
getting required configuration.
237
Fig. 7.1
Fig. 7.2
238
transfer between complex ions, [Fe (CN)6]4- and [Fe (CN)6]3- , initially
the products are in the exited state. If the shapes of reactant – species are
very less distorted, as compared to the transition state, then the energy of
activation required for electron exchange is very less and the reaction is
fast. Although, the value of equilibrium constant for isotopic exchange is
almost same and Go is zero; still energy of activation is required due to
following reasons :
(i) For overcoming electronic repulsion between ions of same charge,
(ii) to distort coordination shells of both the species, and
(iii) to change the arrangement of solvent molecules surrounding the
two species.
K2 = f K1 K2 K
239
where, K1 and K2 are rate constants of the two exchange reactions
and K is equilibrium constant of the overall reaction.
2 In K = In k, + In K
i.e. 2* G1 + * G2 + t Go
(ii) Co (II) complexes are high spin complexes (t2g5 eg2) while Co (III)
complexes are low spin complexes (t2g6 ego); and
240
Deviation from Marcus theory, otherwise considered as if the
reaction is not of outer sphere but is of inner sphere.
241
Here ruthenium complex function as photo-sensitizer. Go = 238
KJ mol-1
When [Ru (bpy)3]2+ absorbs 452 nm light, the very excited state of
initial [** Ru (bpy)3]2+ species changes into quite stable exited
species [Ru (bpy)3]2+ which in comparison to [Ru(bpy)3]2+,
(Ground State Species) is a better oxidant with 2.12 volt (+0.84 V
+ 1.28 V) and with -2.12 V (-0.86 V + 001.26 V) an outstanding
reducing agent (Fig. 7.3)
Fig. 7.3
242
7.6 FACTORS AFFECTING ELECTRON TRANSFER
REACTION RATE
(iii) Fast electron transfer takes place, when due to coupling or by an-
atomic ligand, electrons reach on the surface of the complex.
(v) With the increase in the conductivity of the ligand electron transfer
increases.
(vi) When the difference in the shapes of oxidant and reductant are
much high, then there is possibility of slow reaction.
(vii) Higher is the negative value of Go for the reaction, faster is the
reaction.
243
Check Your Progress-1
Notes : (1) Write your answers in the space given blow.
(2) Compare your answers with those given at the end of the
unit.
a (i) Redox reactions involve ................................. from one atom
to the other.
(ii) Electron – exchange reaction involving no net chemical
change follow ................... electron transfer mechanism and
can be traced by ...................
(iii) The reaction in which electron – transfer results in net
chemical change follow ........................... mechanism and
can be traced by ..................
b (i) For electron – transfer it is necessary that energy of the
participating electronic orbitals ...................
(ii) During electron transfer the ....................... and ....................
of metal ligand bond help in getting required configuration.
(iii) The exited state electron transfer of ............................. opens
the path of the production of hydrogen using solar energy.
244
[NH3)5 Co(H2O)2+ + 5H2O [Co(H2O]2+ + 5 NH3 ...... (7.4)
The intermediate formed in reaction (7.1) dissociates to give a 6-
coordinated (Cr (III) and a 5-coordinated Co (II) Complex [reaction (7.2)]
which then picks up the additional water molecule from the medium
[reaction (7.3)] to develop into a 6-coordinated Co (II) complex. Being
unstable, the Co (II) complex undergoes complete equation to give the
hydrated Co (II) ion [reaction (7.4)].
36
If the reaction is carried out in the presence of Cl- in the
solution, none of this isotope appears in the chromium (III) complex; this
fact provides further support for the bridging mechanism. Because the
change in oxidation states of the metal ions is accompanied by transfer of
a chlorine atom, the process is often referred to as an atom transfer
reaction.
245
There are many other reactions which are believed to proceed by
the inner sphere mechanism. Where all the species involved are too labile
for tracer methods to be applicable or for the mechanism to be inferred
from the nature of the products, dependence of the rate of reaction upon
the concentration of an ion present in the solution can provide useful
information.
(2) The rate cannot be faster than the rate of exchange of the ligand
in the absence of the redox reaction.
(3) The reaction is zero order with respect to one of the complexes
and of first order with respect to the other, where bond
dissociation takes place.
(4) The reaction is first order with respect to the first species if the
rate determining step is the attack on the complex.
246
(5) Electron transfer is rapid only if a conjugated bridged system is
formed in the intermediate.
(7) The rate of reaction between the Cr2+ and between CrX2+ and
between Cr2+ and [Co(NH3)5 X]2+ decreases in the order I- > Br-
>Cl> F- showing that the electron transfer through the bridged
halogen atom affects the reaction rate.
247
7.8 LET US SUM-UP
248
* Electron transfer is expected to be fast when no change in the
molecular dimension takes place and the rate constant depends
upon the cation present in the solution; ion-pair formation
decreases the activation energy by reducing the electrostatic
repulsion energy.
249
* Marcus proposed an approximation, giving an equation for rate
constant of outer sphere electron – transfer reaction.
Marcus relation is –
K2 = f K1 K2 K.
where K1 and K2 are rate constants of two exchange reactions and
K is equilibrium constant of the overall reaction; while f is the
function of rate constants and the interaction rate.
250
* The reaction is zero order with respect to one of the components
(complexes) and of first order with respect to the other, where
bond – dissociation takes place.
251
Unit - 8 METAL-LIGAND EQUILIBRIA IN SOLUTION
Structure
8.0 Introduction.
8.1 Objectives.
252
8.0 INTRODUCTION
You may recall what you have already studied about the basic
concept of chemical equilibria in solution.
8.1 OBJECTIVES
253
describe methods of determining stability constants for binary
complexes in solution.
8.2 STEP-WISE AND OVERALL FORMATION CONSTANTS.
The term stability is a loose term, when the term stability is used
without qualification, it means that the complex exists and under suitable
conditions, it may be stored for a long time. The term can not be
generalised for complexes. A complex may be quite stable to one reagent
and may decompose readily in presence of another reagent.
In studying the formation of complexes in solution, two types of
stability of complexes is found:
1. Thermodynamic Stability
This is a measure of the extent of which the complex will form or
will be transformed into another species under certain conditions,
when the system has reached in equilibrium. When we are
concerned with this type of stability, we deal with metal-ligand
bond energies, stability constant etc.
2. Kinetic Stability
This refers to the speed with which transformation leading to the
attainment of equilibrium will occur. When we are interested in
kinetic stability for complex ions in solutions, we deal with rates
and mechanism of chemical reactions. These reactions may be
substitution, isomerisation, recemisation and electron or group
transfer reactions. In the kinetic sense, it is more proper to call the
complexes inert or labile complex rather than stable or unstable
complex. The complexes in which the ligands are rapidly
replaced by others are called labile, while those in which
substitution occurs slowly are called inert complexes.
254
Stepwise and Overall Formation Constants
According to J. Bjerrum (1941) the formation of a complex in
solution proceeds by the stepwise addition of the ligands to the metal
ion. Thus the formation of the complex MLn may be supposed to take
place by the following n consecutive steps.
where M = central metal cation
L = monodentate ligand
n = maximum co-ordination number for the metal
ion M for the ligand
( ML)
M + L ML K1 = [ M ][L]
( ML2 )
ML ML2 K2 =
[ ML][ L]
( ML3 )
ML2 ML3 K3 =
[ ML2 ][ L]
( MLn )
Thus MLn-1 + L MLn Kn =
[ MLn1 ][ L]
The equilibrium constants, K1, K2, K3, ..........Kn are called stepwise
stability constants.
The formation of the complex MLn may also be expressed by the
following steps and equilibrium constants.
( ML)
M + L
B
ML, =
1
[ M ][ L]
( ML2 )
M +2L
B
ML2, 2 =
2
[ M ][ L]2
( MLn)
Thus M + nL
B
MLn, n =
n
................(8.1)
[ M ][ L]n
255
The higher the value of stability constant for a complex ion, the
greater will be its stability. Alternatively 1/k values sometimes are
called instability constant.
Stepwise and cumulative stability constants are also expressed as
log10K1, log10K2................log10Kn and log10n respectively.
( ML3 )
3=
[ M ][ L]3
[ ML ] [ ML2 ] [ ML3 ]
=
[ M ][ L] [ ML][ L] [ ML2 ][ L]
= K1 x K2 x K3
[ ML ] [ ML2 ] [ MLn ]
Thus n = .............
[ M ][ L] [ ML][ L] [ MLn1 ][ L]
= K1 x K2..........Kn
nn
or n = K
n 1
n
256
8.2.1 Thermodynamic Importance of Stability Constants
In order to reach accurate conclusions regarding the nature of the
forces acting within complex species during their formation in solution,
the energy changes accompanying the reaction in question i.e. a complete
thermodynamic characterisation of the reactions is necessary at the very
least, determination of enthalpy ( H ), entropy ( S ) and free energy
( G )changes accompanying complexation.
S H / T
log K = ......................................................(8.3)
2.303 R
257
In many reactions both the heat and entropy changes favour
complex formation but their relative importance changes markedly with
minor variations from ML to M'L or ML'.
258
almost an entropy effect for the metal ions of nontransitional group, while
for the transitions metals it is partly an enthalpy effect which increases
the crystal field strength. The increase in crystal field strength increases
the points of attachment of the ligand to the metal ion imparting greater
chelating tendency to the latter (cf. CFS). Fig 8.1
The a class metals include H, alkali and alkaline earth metals; the
elements from Sc to Cr, Al to Cl, Zn to Br and lanthanides and actinides.
While amongst b class Rh, Pd, Ag, Ir, Pt, Au and Hg are included.
Elements from Mn to Cu, Tl to Po, Mo, Te, Ru, W, Re, Os, Cd are
border line metals.
259
cation size, comparatively large ionic charge and appropriate electronic
arrangements are responsible for the maximum ability of complex
formation by transition elements.
Mellor and Maley have shown that the stabilities of the complexes
of bivalent metal ions follow the order: Pd > Cu > Ni > Pb > Co > Zn >
Cd > Fe > Mn > Mg irrespective of the nature of the ligand. Irving and
Williams from the analysis of the data on stability constants of transition
metal ions, found that the order
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II),
Univalent ions have not been extensively studied but data on the
complexes of the univalent ions with dibenzol methanate ion shows the
order of the stability as:
260
1. Basicity of the ligands: The greater is the Lewis base strength,
higher is expected to be the stability constant of the complex. Thus
K values for the complexes are expected to change in a manner
similar to the changes in the proton association constant (BH) for
the ligands.
261
interfering resonance interactions are determined by the structure of the
chelating agent. The work of Ley on the chelates of amino-acids showed
that five and six membered rings are the most stable. Much evidence has
accumulated since then to prove that all chelates have either five or six
membered rings. Pfeiffer observed that in general the five membered
rings is the more stable when the ring is entirely saturated but when one
or more double bonds are present, the six membered rings is favoured.
Schwarzenbach and Co-workers have observed that there is a decrease in
clate stability with the increase in ring size. The stability of a five
membered ring is not chiefly due to entropy but rather to the enthalpy of
formation; the example being 1, 2, 3 triamine- propane tetra
chloroplatinum. Further the stability increases with the increase in the
number of rings in the molecule:
M(en) < M(trien) < M(EDTA).
(one ring) (two rings) (five rings)
Steric Effect:
Steric hindrance can influence stability in many ways, e.g.
(i) Metal-ligand bonds are weakened due to the presence of bulky
group near the coordinating site.
(ii) The substituting group prevents the ligand from assuming the
planar configuration and hence introduce strain in the metal-donor
bond.
(iii)Steric hinderacne is also due to strained structure of the chelated
ring, since it breaks the usual linear configuration of the
complexes.
262
Resonance Effects
The stability of a chelated ring will depend on the possibilities of
resonance in the ring and on how these will fit in with resonance in the
organic ligand itself. That resonance may affect the formation of a chelate
was first shown by Calvin and Wilson. The double bond resonance has
been attributed as a reason to be unusual stability of histamine cobalt
chelate.
Orbital hybridisation
There are certain factors which serves to make a specific bonding
arrangement stable. As an example, the shape of , ', ''
triaminotriethylamine is such that the bonding atoms must be grouped
tetrahedral round a metal atom. The ligand will therefore tend to form a
stable complex with a metal such a zinc, which favours sp 3 hybridisation
in its 4-co-ordinate compounds, rather than with one such as copper
which is limited to dsp2 (planar) hybridisation. Similarly, triethylene tetra
amine gives stable complex with metal ions having dsp 2 hybridisation,
rather then sp3 hybridisation.
263
required). Hence the stability constant for metal chelate must be higher.
Consider the equilibrium reactions (Fig. 8.4):
[Co(NH3)6]3+ + 3en [Co(en)3]3+ + 6NH3 ...................(8.4)
Assuming that (i) Co-N bond strength in the two complexes is
same (the f value of ammonia and ethylendiamine are within 3%), and (ii)
the entropy changes due to structure making and structure breaking are
negligible due to the similar size of the complexes, it can be seen that the
o
S will increase for the reaction as the number of moles of the products
are more than those for the reactants. This will help the reaction to go to
the right.
264
8.4 METHODS OF DETERMINATION OF STABILITY
CONSTANTS.
-RT, Ink, = G = H - T S
265
with the reaction. The corresponding changes on entropy change of
complex formation may be obtained by combining the stability constants
with the enthalpy change of complex formation, which is obtained by
determining the stability constant at a series of temperatures. The
knowledge of entropy is essential for the full understanding of many
factors such as size, shape, electronic structure of the central metal and
the ligand, the temperature and the composition of the solvent, which
influence the stability of the complex.
266
the nature of the interacting substances. Thus, it has been used with
success on acid base, and redox equilibria. Although the reactions to be
considered involve ions that are more or less completely hydrated, rather
than the simple ions, but this fact does not affect the validity of the
conclusions, provided the activity of the water is maintained constant.
Let us consider the equilibrium in which an acid and metal ions are
added to a basic ligand in solution. Thus the following equation are
obtained:
[HL ]
L + H+
Ka
HL+, Ka =
[L][H ]
267
Cm = [M+] + [ML+]
Solving the last three equations given above and using the acid
association constant of the ligand, Ka. Then we get
C H [H ]
[ML+] = CL - CH + [H+] -
Ka [H ]
[M+] = Cm - [ML+]
C H [H ]
[L] =
Ka [H ]
Thus on putting the values of [ML+], [M+] and [L] from the above
equation in
[M L ]
K1 =
[M ][L]
268
ligand system (Definitions of the terms n , n A and pL are given
below).
(B) The calculation of the values of formation constants by solution
of the formation function of the system or otherwise.
n term, was introduced by Bjerrum who called it the 'formation
n = Total number of ligand ( L) bound to metal ( M )
Total number of M present in system
n
. i [M Li]
i o
or n = n
.....................................(8.5)
.[M Li]
i o
. i .β[L] i
n = i o
n
[ = 1]................................(8.6)
.β
i o
1 [L] i
A similar function for the proton-ligand sustems is n A, which
defined as the average number of protons bound per not complex bound
ligand molecule, and can be given by.
i
. i .β H
i [H]i
nA = i o
i
[ H
o = 1]........................(8.7)
.β
i o
H
i [L] i
whereas, pL gives the free ligand exponent and may be defined as.
1
pL = log .
[ L]
269
(A) Construction of the Formation Curves:
In Irving Rossotti method, this involves pH-titration of the
following three sets of mixtures (keeping total volume constant) against a
carbonate free standard alkali:
(a) Mineral acid
(b) Mineral acid + Ligand solution
(c) Mineral acid + Ligand solution + Metal ion solution.
The calculation of n are made from the volume of alkali required
to produce the same pH value in the metal and ligand titrations. Similarly
n A values are calculated from the volume of alkali required to produce
the same pH value in the ligand and mineral acid titrations. According to
Irving and Ressotti, n A and n can be expressed as-
(V n V 1 ) ( N E )
Y TLo
nA = (V V 1 )
....................(8.8)
TLo
n = (V V ) (N E ) TL o
iii 1 n ο
....................(8.9)
(Vο V 1 ) n
. TCM ο
Where Vo is the initial volume of the solution, Eo, TLo are the
initial concentrations of the mineral acid and the reagent respectively and
V', V'' and V''' are the volume of alkali of a given normality, N, required
270
during the acid, the ligand and the metal titration respectively at a given
pH (B). While the term Y gives the number of titrable hydrogen ions
arising from the chelating agent and TMo gives the initial concentrations
of the metal.
From the observed values of [L] for each n value, values of pL- are
calculated utilising the equation given by Irving and Rossotti:
n j
1
nH (
anti log
)n
n o V 0 V iii
pL- log10
. ....................(8.10)
Vo
TCL0 n .TCM 0
271
(b) Proton-Ligand formation curve
272
P = Ratio of the concentration of the ligand to the
concentration of metal.
C1 = Molar concentration of metal solution.
X = Concentration of ligand for which the concentration
of complex is maximum.
m = The number of moles of a metal required to combine
with "n" moles of ligand.
X
K=
(a x)(b x)
273
It is assumed that Beer's Law is obeyed, i.e. the optical density of
the solution is proportional to the concentration of the complex in the
given range. If, therefore, any two solutions on the two curves have the
same optical density, as shown in the graph a1, a2 and b1, b2 represent the
concentrations of the metal and the ligand respectively on the two curves,
then:
X X
K= =
(a1 x)(b1 x) (a2 x)(b2 x)
Molar Concentration
Fig. 8.3 :
Taking the concentration a1, a2 and b1, b2 for the same absorbance
i.e., the same value of x, we have
X X
K= =
(a1 x)(b1 2 x) (a2 x)(b2 x)
2 2
274
i.e. AX2 + BX + C = 0
Where, A = 4(a1 -a2 + b1 - b2)
-B = 4(a1b1 - 4a2b2 + b 12 - b 22 )
or b1(4a1 + b1) - b2(4a2 + b2)
C = (a1b 12 - a2b 22 )
By solving the quadratic equation:
( B) ( B 2 4 AC )
K=
2A
( B) ( B 2 4 AC )
K=
2A
By knowing the value of X, the value of K can be calculated.
Similarly, if metal and ligand react in the ratio 2:1 then.
2 M + L = M2 L
Taking the concentration a1, a2 and b1, b2 for the same absorbance
i.e., for the same value of X, we have
X X
K= =
(a1 2 x) (b1 x) (a2 2 x) 2 (b2 2)
2
or 42(a1-a2+b1-b2)-(4a1b1-4a2b2+a 12 - a 22 + (a 12 b- a 22 b2) = 0
i.e. AX2 + BX + C = 0
Where, A = 4(a1 -a2 + b1 - b2)
-B = (4(a1b1 - 4a2b2 + a 12 - a 22 )
or b1(4a1 + b1) - b2(4a2 + b2)
C = (a 1 b 1 - a 12 b 2 )
By solving the quadratic equation, the value of X is determined
( B) ( B 2 4 AC )
K=
2A
( B) ( B 2 4 AC )
or X = 2A
275
3. Mole Ratio Method
The you and jones method can also be utilised for determination of
the stability constants.
Fig. 8.4
the metal or ligand, whichever has the limiting concentration at the point
in question. Therefore
[MX] = A/A extp. C
M = Cm - (mx) = Cm (A/A extp. ) C
X = Cm - (mx) = Cx - (A/A extp.) C
276
[ MX ]
Stability constant K =
[ M ][ X ]
[(A / A extp. ) C]
K=
[(Cm A / A extp. ) C ] [(Cx A / A extp. )C ]
-
277
Check Your Progress-2
278
as : n = K1, K2, K3, ..........................Kn
nn
or n K n
n 1
279
Shape of the ligand molecule also affects stability e.g. while
triethylene teramine gives complex with metal ions having dsp2
I II
hybridisation(sq. planar geometry); , ,
I
while pL is the free ligand exponent; log
[ L ]
280
Turner and Anderson method involves plotting a continuous
variation curve for a given composition and repeating the
procedure for more dilute solutions.
(iii) - RT log K = G = H - T S .
(iv) G is negative.
(v) Mn (II) < Fe (II) < Co(II) < Ni(II) < Cu(II) > Zn(II)
(vi) Entropy factor.
281
Unit - 9 METAL CLUSTERS
Structure
9.0 Introduction.
9.1 Objectives.
9.3 Carboranes.
9.3.1 Synthesis.
9.3.2 Properties.
9.3.3 Structures.
282
9.0 INTRODUCTION
9.1 OBJECTIVES
283
identify compounds with metal-metal multiple bonds and their
structures.
284
Fig. 9.2: B12H12 Icosahedron
285
According to Wade's rule, the building blocks of deltahedrons are
BH units, which are formed by sp-hybridisation of boron atom. Out of the
two sp hybrids one is used in the formation of 2c, 2e B-H exo bond of the
deltahedron and the other sp hybrid is directed inside as a radial orbital.
Remaining two unhybridised p orbitals of each boron atoms are placed
perpendicular to the radial orbitals and are known as tangential orbitals.
These radial and tangential orbitals combine by linear combination
method to form skeleton or framework of the deltahedron. To fill all
bonding molecular orbitals of the skeleton, necessary number of electrons
are obtained form the radial orbitals of BH units and s orbitals of the extra
hydrogen atoms. These electrons are called Skeletal electrons. For
example in B4H10, four BH units contribute 8 electrons (4x2 = 8) and six
extra hydrogens give six electrons thus B4H10 has total 14 skeletal
electrons Fig 9.4 gives the molecular energy diagram of [B 6H6]2-. This
molecule has seven pairs of skeletal electrons (six boron atoms and one
pair from two negative charges). These are used to saturate seven skeletal
molecular orbitals (a1g, t1u and t2g).
tui
eg
t2g
t2u
t2g
t1u
a1g
286
Classification:
On the basis of structures, molecular formula and skeletal electrons
higher boranes are classified into Closo, Nido, Arachno and Hypo (Table
9.1):
Table 9.1
Skeletal
Name Formula Examples
Electron Pair
Closo [BnHn]2- n+1 [B5H5]2- to [B12H12]2-
Nido [BnHn+4] n+2 B2H6 , B5H9, B6H19
Arachno [BnHn+6] n+3 B4H10 , B5H11
Hypo [BnHn+8] n+4 Only derivatives are known.
9.2.3 Nido-Boranes
These boranes have nest (Nido, Latin, meaning Nest) like structure.
Their general formula is BnHn+4 and have (n+2) pairs = 2n+4 skeletal
electrons on removing one boron atom from an apex of closo structure,
nido structure is obtained. Because, of the lost boron atom, these boranes
have extra hydrogens for completing the valency. The polyhedra in this
series have B-H-B bridge bonds in addition to B-B bonds. They are
287
comparatively less stable than 'Closo', but more than 'Arachno' on
heating.
9.2.4 Arachno-Boranes
These boranes have the general formula (BnHn+6) and skeletal
electrons = (n+3) pairs = 2n+6 = electrons. These molecules are obtained
by removing two boron atoms from two apexes of the closo structure and
have spider-web like structure. They have B-H-B bridge-bonds in their
structures and are very reactive and unstable on heating.
Arachno B4H10
Fig. 9.5:
288
This is based on the observation that the structures having same
number of skeletal electrons are related with one another by the removal
of BH unit one by one and the addition of suitable number of electrons
and hydrogen atoms, e.g. by removing one BH unit and two electrons
from octahedral closo. [B6H6]2- ion and adding four hydrogens, we get
square pyramidal nido- B5H9 borane. On repeating same process on nido
B5H9 (i.e. removing one BH unit and adding two hydrogen's), we get
butterfly shaped arachno. B4H10. Each of these three boranes have 14
skeletal electrons, but due to removal of BH unit, the resulting structure
becomes more open gradually (Fig. 9.5). The most symmetrical closo
structure has (n+1) skeletal molecular orbital, which requrie 2n+2
electrons. Similarly, nido-boranes have (n+2) molecular-orbitals and need
2n+4 skeletal electrons; while for (n+3) molecular orbital, arachno
boranes require 2n+6 skeletal electrons (see fig 5.6 for comparison
between these classes of boranes).
9.2.6 Synthesis
The simplest method for synthesis of higher boranes is the
controlled pyrolysis of diborance, B2H6 it is a gas phase reaction, BH3
formed in the first step reacts with borane to give higher boranes:
B2H6(g) 2BH3(g)
B2H6(g) + BH3(g) B3H7(g) + H2(g)
B3H7(g) + BH3(g) B4H10(g)
B2H6(g) + BH3(g) B3H9(g) [B3H8]-(g) + H+
5[B3H6](g) [B12H12]2-(g) + 3[BH4]-(g) + 8H2(g)
2[BH4](g) + 5B2H6(g) [B12H12]2- + 13H2
289
Closp Nido Arachno
9.2.7 Reactions
The important reactions of higher boranes are with Lewis bases,
which involve removal of BH2 or BHn from the cluster, growth of the
cluster or removal of one or more number of protons:
1. Decomposition by Lewis-bases:
B4H10 + 2NH3 [BH2(NH3)2] + [B3H8]
The reaction is analogous to the reaction of diborane with
ammonia.
290
2. Deprotonation :
Higher boranes give deprotonation reaction easily rather than
decomposition:
3. Cluster Building:
Reactions of borane with borohydride are important with
respect to synthesis of higher boranes:
291
Check Your Progress-1
Notes : (i) Write your answers in the space given below .
(ii) Compare your answers with those given at the end of the
unit.
A(i) Metal Clusters include those molecular complexes in which
..............bonds form a....................or large ...............................
(ii) Higher boranes may have different shapes resembling -
(a)
(b)
(c)
(iii) The various types of bonds present in higher boranes are mainly-
(a)
(b)
B(i) Wade's rule relates -
(a)
(b)
and (c)
(ii) Main polyhedral structure of higher boranes is called
............................. which have ....................... units as the building
blocks.
(iii) Main classes of higher boranes with their general formula and
skeletal electrons pairs are -
292
9.3 CARBORANES
Fig. 9.7
2. Nido Carboranes: They are having an open case structure in
which some framework members are attached likely by hydrogen
bridges. These are derived formally from one or other of several
borones.
293
been synthesized with either carbon bridging two boron atoms in a
three centre two electron bond or acting as one end off a hydride
bridge.
First carborane was obtained in 1953 when mixtures of
diborane and acetylene were ignited with a hot wire. Since that
time, many new carboranes have been isolated.
Nomenclature:
Rules for naming carboranes are as follows:
i. First of all, give the positions and number of carbon atoms, then
the type of carborane (either closo or nido) and finally the name of
the borane from which the carborane is formally derived and the
number of hydrogen atoms shown in bracket. For example CB5H9
is name as monocarbonido hexaborane (9). Similarly, the three
isomers of C2B10H12 are named as 1, 2; 1, 7 and 1, 12 dicarbo-
closo-dodecaborane (12).
ii. Number of atoms in these structure are counted by starting the
numbering from that in the apical position and proceeding through
successive rings in a clockwise direction.
This rule is important in naming the isomers.
294
c. dicarbo-closo-dodecaborone
9.3.2 Preparation:
I(a) The Small Closo Carboranes (C2BnHn+2 where n = 3 to 5)
B5H9 + C2H2 490
1,5 - C2B3H5 + 1,6 - C2B4H6 +2,4 - C2B5H7
o
C
(c) Dicarobo-closo-dodecaborone:
Preparation: The orthocarborane is the only isomer which
can be synthesized directly. However, it is synthesized by the base
catalysed reaction of acetylenes with decarborane (14) or via
B10H12L2.
B10H14 + 2L
H
B10H12L2
2
R2L2B10H10 + H2 + 2L
RC 2 2
295
Example: B5H9and C2H2 undergo reaction in the gas phase at 215oC
to give mainly the nidocarborane 2,3 - C2B4H8 together with methyl
derivatives of CB5H9.
The preparation method described above does not yield a
single product but a mixture of several products whose separation is
not an easy task. However some smaller nidocaroranes are prepared
by the following specific methods:
i. Mono carbo-nido-hexaborane (7) CB5H7 is formed by
passing silent electric discharge through 1-methyl
pentaborane (9).
ii. The only example isoelectronic with B5H9 is 1,2-
dicarbonido - pentaborane(7), C2B3H7, which is prepared as
follows:
B4H10 + C2H2 50
C2B3H7 (3 - 4 % yield)
o
C
Large Nido-Carborane:
Dicarbo-nido-undecaborane, C2B9H13, is the second member
of the class of nido-carboranes C2BnHn+4 (n =4 or 9),. The parent
carborane and its substituted derivatives can be prepared by the
base degradation of ortho-carborane (1,2-dicarbocloso-
dodecaborane (C2B10H12).
1
1,2 - C2H10H12 C2B9H12
MeO
C2B9H13
H
296
9.3.2 Properties
Properties of carboranes resemble with that of the corresponding
boranes closely. Thus, 1.2 dicarbo closo-dodecarborane-12 is stable in
both air and heat. On heating in inert atmosphere at 500 oC, it is converted
into 1, 7 isomer i.e. meta or neo isomer; while at 700 oC it is concerted to
1, 12 isomer i.e. para-isomer (Fig. 9.8)
All three of the icosahedral isomers are stable both to heat and to
chemical attack, and much more so than decaborane (14). They are white
crystalline solids which resist both strong oxidizing agents and strong
reducing agents and are also stable to hydrolysis. This is important
because it allows reactions to be carried out on substitutions, often under
quite drastic conditions, without destroying the cage structure, rather as
297
the chemistry of derivatives of an aromatic ring such as benzene can be
developed without destroying the ring.
+ -
C2B4H8 + NaH Na C2B4H7 + H2
diglyme
298
9.3.3 Structures
Structural studies of carboranes have been done using X-ray
analysis and nmr studies.
The C2B3, C2B4 and C2B5 closo-carboranes, for example, have
trigonal bipyramidal, octahedral and pentagonal bipyramidal skeletal
structrues respectively, and positional isomers have been identified.
The icosahedra structure is similar to that of B 12H122- (Fig. 9.8) and
is electron-deficient, with electron delocalization extending over the
whole framework. It is thus in effect a three-dimensional aromatic
molecule, with marked electron withdrawing character, the most
important result of which is to render the two hydrogen atoms bonded to
carbon acidic. All the C-H and B-H bonds are of the normal two-electron
type and the electron deficiency is associated with the framework, in
which there are multicentre bonds.
The Structure of nido C3B3H7 is shown in Fig. 9.9. In the diagram
hydrogen bridges are shown by curved lines, but terminal B-H and C-H
bonds are ommitted. It can be seen that the introductions of successive
carbon atoms to the framework involves the elimination of one bridge
hydrogen atom and one B-H (i.e. the replacement of BH2 by an
isoelectronic CH unit). Like all the carboranes these compounds are
electron-deficient, with multicentered bonds and delocalization extending
over the entire framework. In much the same way, C2B3H7 has a square
pyramidal structure that is formally derived from that of B 5H9, with two
BH2 replaced by 2CH.
Fig. 9.9
299
9.4 METALLO-BORANES AND METALLO CARBORANES
300
2[C2B9H11]2- + FeCl2 [(C2B9H11)2Fe]2- + 2Cl-
[C2B9H11]2- + BrRe(CO)5 [C2B9H11.Re(CO)3]- + Br- + 2CO
[C2BgH11]2- + BrMn(CO)5 [C2B9H11.Mn(CO)3]- + Br- + 2CO
301
On the basis of Wade's rule, the structrues of these metal
derivatives may be known from their molecular formula and skeletal
electrons. For example in B3H7[Fe(CO)3]2, n=5 (3B + 2Fe) and skeletel
electrons are 14. Hence it has nido structure corresponding to square
pyramidal (Fig. 9.12).
9.4.1 Properties
Just as the carboranes, lithio and Grignard's derivatives of metallo
carbones give substitution reactions of organometallics, which include:
(a) Formation of derivatives such as carboxylic acids, ester, alcohol,
ketone, amines etc.
(b) Synthesis of iodo and nitroso devivatives.
(c) Elmination of Lithium halide-
PCl3 + C2PhL2B10H10 (C2PhB10H10)2Pl
Ph3PAuCl + C2RLiB10H10 Ph3AuC(Cr)B10H10l
l l
- B10H10 -
OC CO
Ni
(C6H5)2 PC CP (C6H5)2
B10H10
302
Similarly, derivatives of mercury and other metals( -bonded) have also
been obtained,
RC2LiB10H10 B10H10RC2HgC2RB10H10
H Cl 9 2
303
Table 9.2
No. of Geometry Metal Bonding No. of Examples
Metal Skeleton Molecular Cluster
Atoms Structure Orbital electron
1. Monomer 9 18 Ni(CO)4
2. Dimer 17 34 Fe(CO)9,
Mn2(CO)10
3. Triangle 24 48 Os3(CO)12,
Co3(CO)9CH
4. Tetrahedron 30 60 Co4(CO)12,
Rh4(CO)12
Butterfly 31 62 Re4(CO)162-,
[Fe4(CO)12C]2-
Square 32 64 Os4(CO)16,
Pt4(O2CMe)8
5. TBP 36 72 Os5(CO)16
Octahedral 37 74 Fe5(CO)15C
6. Trigonal 43 86 Ru6(CO)17C
prism
7. 45 90 [Rh6(CO)15C]3-
304
Tetrahedron Butterfly Square Planar
Fig. 9.13
Synthesis:
1. Pyrolytic Synthesis:
2CO2(CO)8 CO4(CO)12 + 4CO
2. Redox Condensation:
[Ni6(CO)12] + 4CO
Ni(CO)4 + [Ni5(CO)12]2- 2-
Reactions:
1. Substitution Fragmentation:
Fe3(CO)12 + P.Ph3
Fe3(CO)11(Ph3) + Fe3(CO)10(P.Ph3)2 +
2. Prolongation:
[Fe3(CO)11]2- + H+
[Fe3H(CO)11]
-
305
9.5 Metal Halide clusters
Although the first information of metal halide clusters was given in
12th Century in the form of calomel, but dimeric nature of mercurous ion
could be established in 20th Century only. But now number of metal
halide clusters are known.
Dinuclear Complexes:
Most important dinuclear species is [Re2X8]2- (Fig. 9.14).
306
The structures of these dinuclear complexes are either similar to
ethane or an edge-shared bioctahedron or a face shared bioctahedron (Fig.
9.15). or tetragonal prism (Fig. 9.14).
Trinuclear Cluster:
The well known examples of trianuclear cluster are rhenium
trichloride, [ReCl3]3 or Fe3Cl9 and their derivatives. Rhenium Chloride is
a trimer, and has been used for the preparation of other trimers as a
starting material. Its structure is shown in Fig. 9.16.
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Hexanuclear clusters:
Hexanuclear Clusters or Mo, Nb and Ta halides are well known.
Two species are known, one with molecular formula M6X12 or [M6X8]X4
and the other with molecular formula [M6X14]2-.
Molybdenum forms cluster of the type [M6X8]X4. [M6X8]4+ ion has
an octahedral skeleton of metal atoms, each face of which is coordinated
with a chloride ion (Fig. 9.17).
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Fig. 9.19: Structure of [M6X18]2+
Fig. 9.20
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Chevrel-phases :
Chevrel phases generally involve tertiary molybdenum
chalcogenides, MxMoX6, polynuclear clusters, which have characteristic
properties (specially electrical and magnetic). Their structures are also
abnormal. An important example of these phases is a super-conducter
substance, PbMo6S8. Its structure consists of an octahedral cluster of
molybdenum atoms, which is surrounded by cubic cluster of sulphur
atoms. Then this whole structure is enclosed in to a cubic structure of lead
atoms. The internal Mo6S8 cubic structure rotates with respect to lead
lattice. This rotation is due to strong repulsion between sulphur atoms.
Similarly, the superconductivity originates due to overlapping of d-orbital
of molybdenum (Fig. 9.21).
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These species were designated as Zintle anions and cations. These
are homopoly atomic species, which have no ligands attached with. (Fig.
9.22)
311
Table 9.3 gives important informations about the complexes having
metal-metal multiple bonds.
Table 9.3
Complex Electronic Bond Order Bond
Configuration Length
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Check Your Progress -2
Notes : (1) Write your answers in the space given below.
(2) Complex your answers with those given at the end of
the unit.
(a) (i) carboranes are......................of carbon and boron having both
these atoms in an...........................skeletal frame work.
(ii) The important example of carboranes is........................which
is isoelectronic with..........................................
(iii) The isomeric compounds of 1, 2 dicarbocloso decabrone 12
are -
(i) ........................................
and (ii) ........................................
(iv) [C2B9H11]2- ion reacts with FeCl2 and BrRe(CO)5 to give-
(i) ........................................ and
(ii) ........................................ respectively.
(v) Rh6(CO)16 has total ............................. electrons ...................
electrons per rhodium atom are used for ....................
bonding and remaining ..................... electrons (= )
pair electrons indicate......................structure.
(vi) In [Nb6Cl12L6]2+ crystals ..................... ligands are present
on ....................... of the ........................... skeleton of metal
atoms and remaining ........................ ligands are attached to
............... atoms.
(vii) Compounds with metal-metal multiple bonds are given by
........................ in .......................... block series, in their
................ oxidation states.
(viii) Example of -
(i) Chevrel phase is ........................................
(ii) Zintle anion is .......................... and ....................
(iii) Oxalate complex is ........................................
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9.7 LET US SUM UP
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Arachno, [BnHn+6], with (n+3) skeletal electron pairs,
and Hypo, [BnHn+8], with (n+4) skeletal electron pairs,
Removal of one BH unit and 2 electrons from octahedral closed
[B6H6]2- ion and adding four hydrogen atoms gives square
pyramidal nido B5H9 borane. On repeating same process on nido
B5H9, butterfly shaped arachno B4H10 is obtained. Each of these
three boranes has 14 skeletal electrons, but removal of BH unit
gradually results in more and more open structure.
The bronsted- acidity of boranes increases with their size:
B4H10 < B5H9 < B10H14
Carboranes are mixed hydrides of C and B having both these atoms
in an electron defficient skeletal framework. They are classified in
to closo and nido-carboranes accordingly.
Important member of carboranes is B4C2H6 which is isomeric with
[B6H6]2-.
Properties of Carboranes resemble with those of the corresponding
boranes. Thus 1,2-di-carbo closo dodecarborane -12 is stable in
both air and heat. Its meta and para isomers are 1,7 C2B10H12 and
1,12 C2B10H12 respectively.
Borane and carborane clusters in which metals are present are
known as Metalloboranes and Metallo carboranes Closo-
B10C2H12 reacts with butyl lithium or grignard's reagent to give
lithium and magnesium metallocarbornes.
Similarly [C2B9H11]2- reacts with FeCl2, BrRe(CO)5 or
BrMn(CO)5 to give Fe, Re or Mn derivatives.
On the basis of wade's rule the structures of these metal derivatives
may be known from their molecular formulae and skeletal
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electrons e.g. B3H7 [Fe(CO)3]2 with n=5 (3B+2Fe) and skeletal
electron 14 is nido-metalloborane with square pyramidal geometry.
Skeletal electrons in metal carbonyl and halide clusters are
counted using Wade-Mingos-Lauher-rule. In this method the total
number of valency electrons in all the metal atoms present in the
complex are counted and then electrons donated by ligands are
added. Thus in Rh6(CO)16 -
6 Rh = 6 x 9 = 54e-
16 CO = 16 x 2 = 32e-
Total = 86e-
Out of these 86e-, 12 per Rh atom are used for the non-frame
work bonding and remaining 14e- are used for skeletal-bonding.
These include (n+1) e--pairs; hence it has closo-structure.
Important examples of metal halide crystals are [ReCl8]2-, [W2Cl9]3-
, [ReCl3]3 dimeric [Mo2Cl8]4- and [Mo6Cl8]4+.
In [Nb6Cl12L6] type clusters, 12 Cl- ligands are present on 12 edges
of the octahedral skeleton of metal atoms and remaining 6 ligands
are attached to six metal atoms.
Compounds with metal-metal multiple bonds may be either chevrel
phases (e.g. PbMo6S8) Zintle anions or cations (e.g. Sn94-, Pb74-,
Bi95+, Te64+ etc) or metal-metal polybonded complexes.
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(c) Spider's web
(iii) (a) 2c, 2e bonds
(b) 3c, 2e bonds
(B) (i) (a) Number of electrons in the molecule.
(b) Their formula, and
(c) Shapes.
(ii) Called Deltahedron
Which have BH units.
(iii) Name Formula Skeletal electron-pairs
(a) Closo [BnHn]2- (n+1)
(b) Nido [BnHn+4] (n+2)
(c) Arachno [BnHn+6] (n+3)
2(i) Mixed hydrides in an electron defficient.
(ii) C2B10H12
with B12H12
(iii) (i) 1, 7 C2B10H12 (meta isomer)
(ii) 1, 7 C2B10H12 (para isomer)
(iv) (i) [(C2B9H11)2Fe]2- and
(ii) [C2B9H11Re(CO)3]-
(v) 86 electrons.
12 electrons for
non frame work bonding
remaining 14 electrons (=n+1) pairs indicate closo structrue.
(vi) 12 ligands
on 12 edges of the
octahedral skeleton
to six metal atoms.
(vii) Earlier metals in d-block
in their lower oxidation states.
(viii) (i) PbMo6S8
(ii) Sn94-, Pb74- and Sb73-
(iii) [Mo2(CH3OO)4]
317