Bonding g in Coordination Compounds p

Valence Bond Theory (VBT) Crystal Field Theory (CFT) Molecular Orbital Theory (MOT)

Valence Bond Theory (VBT)

Lewis bases (ligands) Lewis acids (metals or metal ions) The metal utilizes hybridization of metal s, p, and d valence orbitals to account for the observed structures and magnetic properties of complexes.

Pt2+
2 PtCl42-

[Xe]4f145d8

dsp2 hybrid orbitals electrons from Cl-, square planar

Ni2+ NiCl42-

[Ar]3d8

sp3 hybrid orbitals electrons from Cl-, tetrahedral

Co3+ CoF63-

[Ar]3d6

sp3d2 hybrid orbitals electrons from F-, octahedral

Co3+

[Ar]3d6

Co(NH3)63+

d2sp3 hybrid orbitals electrons from NH3, octahedral

Bonding in coordination complexes

Crystal Field Theory is an electrostatic approach where we treat the ligands as point negative charges and ask ourselves what the effect of repulsion between these charges h and d the th d-electrons d l t on the th metal t l ions i will ill be. b Explains many of the basic physical properties of transition metal complexes but not all of them Molecular orbital theory is more complex than crystal field theory, theory but it allows a more complete explanation of the observed physical properties.

Crystal Field Theory (CFT)

1929, Hans Bethe As originally conceived, it was a model based on a purely electrostatic interaction between the ligands and the metal ion. 1935, modifications J.H. Van Vleck allow some covalency in the interaction

Ligand Field Theory (LFT) 1950, apply CFT to transition metal complexes successful in interpreting many important properties of complexes symmetry consideration identical to MOT

Splitting of the d orbitals by an octahedral field eg

3/5o 10Dq 2/5o

t2g [Ti(H2O)6]3+ t2g1eg0 Purple 243 kJ/mol (o) d1 t2geg1
1.0

log

0.5

0.0

20,300 cm-1 Frequency

Crystal Field Stabilization Energy (CFSE)

Weak field o < P (pairing energy) High spin

Strong field o > P (pairing energy) Low spin

Weak field e d1 d2 d3 d4 d5 d6 d7 d8 t2g1 t2g2 t2g3 t2g3 eg1 t2g3 eg2 t2g4 eg2 t2g5 eg2 t2g6 eg2 1 2 3 4 5 4 3 2 CFSE 0.4 o 0 8 o 0.8 1.2 o 0.6 o 0.0 o 0.4 o 0.8 o 1.2 o

Strong field e t2g1 t2g2 t2g3 t2g4 t2g5 t2g6 t2g6 eg1 t2g6 eg2 1 2 3 2 1 0 1 2 CFSE 0.4 o 0 8 o 0.8 1.2 o 1.6 o 2.0 o 2.4 o 1.8 o 1.2 o

Splitting of the d orbitals in a tetrahedral field t2

2/5t 3/5t
e

t = 4/9 o (high spin)

Splitting of the d orbitals in a square planar field (d8) x2- y2 x2- y2 eg z2 b1g

xy

b2g

xy z2 t2g xz, yz xz, yz Ni(CN)42- , PdCl42-, Pt(NH3)4 , PtCl4 , AuCl4Removal of z ligands

2+ 2-

a1g

eg

Factors Affecting the Magnitude,

1. Oxidation state of the metal ion Ru(H2O)62+ o = 19800 cm-1 Ru(H2O)63+ o = 28600 cm-1 Nature of the metal ion 3d < 4d < 5d Number and g geometry y of the ligands g Td = 4/9 oh Nature of the ligands I- < Br- < S2- < SCN- < Cl- < N3-, F- < urea, OH- < ox, O2- < H2O < NCS- < py, NH3 < en < bpy, ohen < NO2- < CH3-, C2H5- < CN< CO o = f g f : field strength of a ligand relative to water (1.00), 0.7 - 1.7 g : characteristic of the metal ion, 8000 36000 cm-1

2. 3. 4.

Crystal C ysta Field e d Theory eo y

Consider the ligands g are p point negative g charges or as dipoles. How do these charges interact with the electrons in the d-orbitals?

Bonding in Complex Ions: Crystal Field Theory

Consider bonding in a complex to be an electrostatic attraction between a positively charged nucleus and the electrons of the ligands ligands.
Electrons on metal atom repel electrons on ligands. ligands Focus particularly on the d-electrons on the metal ion.

Octahedral complexes p
Two of the d-orbitals point towards the ligands Repulsion between the ligand electrons and electrons in these two d-orbitals destabilizes them

oct is referred to as the ligand g field splitting p g for the octahedral complex

Octahedral Complex p and dOrbital Energies

Electron Configuration in dOrbitals

P

Hunds rule > P low spin d4

pairing energy considerations < P high spin d4

W k and Weak d St Strong Field Fi ld Li Ligands d

Two d6 complexes:

Energy Effects in a d10 System

Ligand field splitting

The ligand field splitting depends upon the metal, t l th the oxidation id ti state t t of f th the metal, t l and d th the ligand type High oxidation state favors large Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mn4+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+ Effect of ligand is given by the spectrochemical series I- < Br- < S2- < SCN- < Cl- < NO3- < F- < OH- < 2- < H O< NCS- < CH CN < NH < en < C2O42 2 3 3 bipy < phen < NO2- < PPh3 <CN- < CO

Spectrochemical Series
Large Strong field ligands CN- > NO2- > en > py NH3 > EDTA4- > SCN- > H2O > ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > IS Small Weak field ligands

Ligand field splitting parameters

Tetrahedral complexes
Three Th of f th the d d-orbitals bit l point i t almost l t towards t d the th
ligands. The other two point between the ligands Repulsion between the ligand electrons and electrons in the three d-orbitals that almost point i at the h ligands li d destabilizes d bili them h

For a given ligand-metal combination, t should be smaller than the o (4/9ths) as there are fewer ligands in the tetrahedral complex and none of them point directly at the d-orbitals

Tetrahedral Crystal Field

Square Planar Crystal Field

Factors effecting spin state

Both and the spin pairing energy depend upon the metal and the ligands. ligands - High field ligands, CN- etc, high metal oxidation state, and metals from the 4d and 5d series all favor large and hence the formation of low spin complexes Tetrahedral complexes can also in principle occur in high and low spin forms. - As t is al always a s less than o, other othe things being equal, nearly all tetrahedral complexes are high spin

High spin-low spin equilibria

Some coordination
complexes show a phase transition from high to low spin as a function of temperature This has been used as a means of information storage for prototype smart cards! Transition presumably occurs because is slightly temperature p dependent p in the solid state

Experimental p methods for determining g the spin state

The spin state of a complex influences both the absorption spectrum and the magnetic properties of the species Absorption spectra are usually harder to interpret than magnetic data Both the orbital and spin angular momenta of the electrons influence the magnetic properties of f a sample l - But in coordination complexes the orbital contribution can often be ignored

Magnetic Properties of Coordination Compounds and Crystal Field Theory.

Paramagnetism illustrated:

Interpreting magnetic measurements

Th The magnetic ti susceptibility tibilit () is i measured d as a f function ti of temperature A magnetic g moment () for each metal ion can be obtained from the magnetic susceptibility - We can think of the unpaired electrons on each atom as behaving b h i lik like a littl little b bar magnet. t Th The magnetic ti moment of an atom or ion is a measure of how strong this bar magnet is. Theoretically, for spin only systems = 2 [S(S+1)]1/2 B - B (Bohr magneton) are the units in which the magnetic ti moment t () ( ) is i given i - S is the total spin angular momentum. It tells you how many unpaired electrons there are S = 0.5n, where n is the number of parallel spin unpaired electrons in the ion

Magnetic properties
Magnetic susceptibility measurements can be used to tell if a complex is high or low spin They can also be used to distinguish between square q planar p and tetrahedral geometries. g Square planar complexes are nearly always low spin d8 (diamagnetic). If a four coordinate compound is paramagnetic it is probably tetrahedral 2- (square planar) is diamagnetic, - e.g. e g Ni(CN)42 diamagnetic but NiCl42- (tetrahedral) is paramagnetic

Color and the Colors of Complexes

Primary colors:
Red (R), green (G) and blue (B).

Secondary colors:
Produced by mixing primary colors.

Complementary C l t colors: l
Secondary colors are complementary to primary. i Cyan (C), yellow (Y) and magenta (M) Adding a color and its complementary color produces white.

Effect of Ligands on the Colors of f Coordination C di ti C Compounds d

Colors
The colors of most transition metal complexes arises as a consequence of the ligand field splitting

Electronic spectra
T Transition i i metal l complexes l with i h more than h one d electron often show absorption bands at multiple wavelengths not just one transition corresponding to The appearance of multiple bands is due to electron-electron repulsion may have more than one state for a given electron configuration

Lattice energies of 3d oxides

Double humped trend due to CSFE and high spin ions