Escolar Documentos
Profissional Documentos
Cultura Documentos
Pilkington
General Convention
The word ligand is derived from the Latin verb ligare meaning to
bind.
In a complex
p we have a Lewis Acid Base interaction:
An arrow is used to show the donation of an electron pair from a
neutral ligand to an acceptor.
A line is used to denote the interaction between an anionic ligand and
the acceptor.
Often however, this convention is ignored and a line to denote both
types of interaction is used.
F example:
For l
Co3+ Cl Co3+
1
NH3 3+
Each N atom donates a pair of electrons to the Co3+ metal ion, i.e. each
NH3 molecule is a Lewis base while the metal ion is the Lewis acid.
We think of the metal to ligand interaction as being essentially covalent,
but in reality this is not entirely true as the character of metal-ligand
interactions varies with the nature of the metal ion and the ligand.
3+ 3+ 3+
NH3
NH3 NH3
H3 N NH3 H 3N NH3 H3N NH3
Co or Co or Co
H3N NH3 H3N NH3
H 3N
NH3 NH3
NH3
NH3
complex:
+ +
H3 N NH3 H 3N NH3
Co3- Co3+
+ H 3N NH3
H3N +
NH3
+NH NH3
3
(a) (b)
Coordinate bonds are formed by lone pair donation from the ligands
the Co3+ centre.
It implies transfer of charge from ligand to metal and figure (a)
shows the resulting charge distribution. This is unrealistic since the
Co3+ centre becomes more negatively charged than would be
unfavorable given its electropositive nature.
At the other extreme, consider bonding in terms of an ionic model
(b) the 3+ charge remains localized on the cobalt and the six NH3
(b),
ligands remain neutral. However this model also does not agree with
experimental studies on this complex. So this model is flawed.
Neither model is appropriate.
2
+
1/2
NH3 3+
1/2 + +
1/2
H3N NH3
Co0
1/2 + +
1/2
H3 N +
1/2 NH 3
NH3
Co3+ Cl Co3+
This representation shows that a bridging chloride ion donates two pairs
of electrons to two Co3+ metal ions which are the Lewis acids, accepting
the lone pairs.
In reality,
lit when
h n thinking
thinkin about
b t ththe b
bonding,
ndin ththe formal
f m l charge
h on
n the
th
chloride ion is not actually -1, which means also that the formal charge
on the two Co3+ metal ions are not strictly +3. either.
What is important is that we have a complex above which has an overall
charge of +5. In order to easily determine the overall charge of the
complex, the above representation is easy to use (3+3-1 = 5).
With respect to thinking about the coordinate bond it does not however
accurately represent the formal charges on the metal ions and the
ligands.
This is analogous to a C-Cl bond in organic chemistry, we write C-Cl but
in reality this does not accurately describe the bonding interaction
since the electrons are not evenly shared and the truth is C+Cl-.
3
Determination of Formal Oxidation States of Metals
in Coordination Complexes
H2 C CH2
CH3CH2CH=CH2
H2 C CH2
4
2. Stereoisomers not only have the same formulas but also the
same connectivities of their atoms. The spatial arrangements
of the atoms are different. There are two examples:
H H H3C H
cis trans
H H
C C
F I I F
Cl
Cl
5
2. Isomerism in Transition Metal Complexes
Structural Isomers
There are many types of structural isomers in transition metal
complexes. We will explore three of them.
g
1. Ionization isomers - Ligands inside the coordination sphere
p
exchange places with ligands outside the coordination sphere.
Ionization isomers are so-named because they give different ions
when dissolved in water.
Example: There are three compounds with the formula
CrCl3.6H2O. One is violet, one is grey-green, and the third is deep
green.
The violet isomer produces 3 moles of silver chloride upon
reaction with silver nitrate, and does not lose water in a
desiccator.
[Cr(H2O)6]Cl3 (violet)
Note that the chloride ions that react with silver nitrate are
the ones not bonded to the chromium(III) ion, and the water
molecules that are lost in a desiccator are the uncoordinated
ones.
6
2. Linkage isomers - Linkage isomers can exist when one or more
ambidentate ligand is bonded to a metal ion.
O N O O N O an ambidentate ligand
7
3. Coordination isomers - involve ligand exchange between
coordination spheres of two metal ions that are part of the
same compound.
[Pt(NH3)2Cl2] has the same ratio of atoms, but does not have
the same overall formula; hence it is not a coordination isomer
of the above compounds.
8
An example of geometric isomers in octahedral complexes are
the cis- and trans-isomers of the
tetraamminedichlorocobalt(III) ion:
Geometric Optical
1. Ionization cis/trans (enantiomers)
2. Linkage
3. Coordination