Bonding in Transition Metal Complexes

Bonding in Transition Metal Complexes: Crystal Field Theory

Proposed by physicists to account for differences between magnetic and spectroscopic properties of transition metal ions as: i) free ions ii) when surrounded by ligands Crystal field theory is an electrostatic model. Uses ligand electrons to create an electric field around the metal centre Ligands are treated as point negative charges which are attracted to the positively charged metal The (negatively charged) electrons of the metal and the negative ligands repel each other Z There are no metal-ligand covalent interactions Consider an octahedral complex, with a first row metal cation surrounded by six ligands.
Y

M+

What it succeeds in explaining

Colour due to the presence of d-d transitions in electronic spectra of complexes (not possible for free ions) Magnetic properties of complexes Metals with the same d electron count can give complexes with different numbers of unpaired electrons (high spin/low spin), e.g. [Fe(H2O)6]2+ and [Fe(CN)6]4 It ignores covalent interactions , however these have been taken into account in the more advanced LIGAND FIELD THEORY.

Bonding in Transition Metal Complexes: Crystal Field Theory

But the distribution of ligands around the metal d-orbitals is not spherically symmetric Electrons in some orbitals are more stable than in others Those which point along the axes (dx2-y2 and dz2) are less stable than those which point in between the axes (dxy, dxz and dyz)

The Octahedral Crystal Field

If the electrostatic field (the crystal field) were spherical, then the energies of the five 3d orbitals would be raised(destabilised) by the same amount. However, dz2 and dx2-y2 atomic orbitals are destabilised to a greater extent than the dxy, dyz and dxz atomic orbitals.
5

The five d-orbitals in an octahedral field of ligands.

Splitting of d-orbital energies by an octahedral field of ligands.

is the splitting energy

Crystal field theory predicts that the d orbitals in a metal complex are not degenerate. The pattern of splitting of the d orbitals depends on the crystal field, this being determined by the arrangement and type of ligands.

The Octahedral Crystal Field

Repulsion by six ligands in an octahedral complex splits the d orbitals on the central metal into t2g and eg levels. In an octahedral field the two sets of d orbitals are labeled eg (doubly degenerate level) and t2g (triply degenerate level) The energy separation between the sets of orbitals is O (octahedral crystal field splitting)
9

d-orbital splitting diagram

Implications and Magnitude of the Crystal Field Splitting

[Ti(H2O)6]3+ eg

d1

t2g

An electron in one of these orbitals is stabilised by an amount of 2/5 O. This stabilisation is referred to as the crystal field stabilisation energy (ligand field stabilisation energy). The crystal field stabilisation energy is a measure of the net energy of occupation of the d orbitals relative to their mean energy. For t2gxegy configuration: CFSE = (-0.4x + 0.6y)o
10

d1 (Ti3+)
eg

d2 (V3+)
eg

d3 (Cr3+)
eg

t2g

t2g

t2g

CFSE = -2/5O

CFSE = -4/5O

CFSE = -6/5O

[Ti(H2O)6]3+ d4 (Mn3+)
eg

[V(H2O)6]3+

[Cr(H2O)6]3+ d5 (Fe3+)
eg

t2g

t2g

CFSE = (3 x -2/5O) + 3/5O = -3/5O

CFSE = ???

[Mn(H2O)6]3+

[Fe(H2O)6]3+

11

o values for some [MLn]n+ complexes

12

Values of CFSE

13

Problem-Solving in Coordination Chemistry The order observed in the spectrochemical series for ligands is as listed in question 1. How many unpaired electrons would you expect to find in the complex ion, [Cr(CN)6]3-, if the values of the splitting parameter is as large as it is in typical cyanide complexes?
14

[Cr(CN)6]3eg

Cr3+ : d3

d-orbital splitting diagram d-electron configuration: t2g3 eg0

t2g

Paramagnetic; 3 unpaired electrons

15

Colours of transition metal complexes

If the lower d-orbitals are occupied and the upper orbitals are vacant or partly vacant, an electronic transition (energy jump) from the lower level to the higher may occur. This energy jump is termed a d d transition and it usually absorbs light in the visible region of the electromagnetic spectrum. The colour of the complex will depend on the magnitude of .
16

The color of [Ti(H2O)6]3+

17

Colours of transition metal complexes

Since for the absorption of a light photon:
o = E = h = hc/

If we can measure the of light absorbed we can determine the E (which corresponds to o).

18

19

20

Variations in Crystal Field Splitting

Ligands which cause only a small degree of crystal field splitting are termed weak field ligands. Ligands which cause a large splitting are called strong field ligands. Common ligands can be arranged in ascending order of crystal field splitting (determined spectrophotometrically). This series is called the SPECTROCHEMICAL SERIES.

Weak Field (small o)

I < Br < SCN < Cl < NO3 < F < (O2 OH H2O) < NCS < NH3 < bipy < CN < PR3 < CO
Strong Field (large o)
21

The Spectrochemical series.

For a given ligand, the color depends on the oxidation state of the metal ion. For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO WEAKER FIELD SMALLER LONGER STRONGER FIELD LARGER SHORTER

22

Other Factors Affecting Crystal Field Splitting

values increase with an increase in the oxidation state of the metal ion.
Smaller ion occurs with a higher oxidation state Smaller ion leads to shorter M-L bond distances

values for corresponding complexes of metal ions in the same group and with the same oxidation states increase by 30 50% on going from the first row transition metal to the second row transition metal ion and by the same amount again from the 2nd row to the 3rd row transition metal ion.
Better M-L bonding occurs with 4d and 5d orbitals

values will vary across any transition metal series. The splitting is dependent on the stereochemistry of the complexes
23

Weak and Strong Crystal Fields

d1 eg
d2 eg
d3 eg

t2g

t2g

t2g

eg

d4

eg

HIGH SPIN Weak field Spin-free

t2g
t2g

LOW SPIN Strong field Spin-paired

Ligands with strong interactions to the metal are called strong field ligands. Ligands with small interactions with the metal are called weak-field ligands.
24

The effect of ligand on splitting energy.

25

 Arrangement which occurs for any particular complex depends on whether the energy to promote an electron to the upper eg level is greater than the energy to pair electrons in the lower t2g level. The amount of crystal field splitting is determined by the strength of the ligand field. A weak field ligand (Cl-) will only cause a small splitting of the energy levels. Thus it will be more favourable energetically for electrons to occupy the upper eg level and have a high spin complex, rather than to pair electrons.
26

Crystal Field Stabilisation Energy: High- and Low-spin Octahedral Complexes

27

High-spin and low-spin complex ions of Mn2+.

28

Orbital occupancy for high- and low-spin complexes of d4 through d7 metal ions.
high spin: weak-field ligand low spin: strong-field ligand high spin: weak-field ligand low spin: strong-field ligand

29

 Question: How can we show that we have high spin or low spin complexes? Answer: By making magnetic measurements, we can measure the magnetic susceptibility of a sample of a metal complex using a GOUY balance.

30

Magnetic Properties
Atoms, ions or molecules with one or more unpaired electrons are attracted in a magnetic field, i.e. they are paramagnetic. The quantity used as a measure of the force exerted by the field on a unit mass of a specimen is referred to as the magnetic susceptibility g .

31

 Each atom or ion or molecule behaves as a micromagnet. The magnetic field produced by these micromagnets an be expressed in terms of a quantity called a magnetic moment. The molar magnetic susceptibility m of a material is related to the magnetic moment according to the equation: = 284( mT) T = temperature m = g x molar mass
32

 What we measure is the spin-only magnetic moment, . = 2{S(S+1)} B where S is the total spin quantum number and S = n/2, where n is the number of unpaired electrons. B is a collection of constants known as the Bohr magneton. = {n(n+2)} B

33

 By measuring the magnetic moment, we can infer the electron configuration. Thus for n = 2, = {n(n+2)} B = {2(2+2)} B = 8 B = 2.83 Bohr magnetons What is the electron configuration of an octahedral Co(II) complex which has a magnetic moment of 4.0 B? The magnetic moment of the complex [Mn(NCS)6]4- is found to be 6.06 B. What is its electron configuration?
34

Values of (spin-only)

35

The Jahn-Teller Effect

Definition: Any non-linear molecule in a degenerate electronic state will distort so as to remove that degeneracy
For a tetrahedral metal ion in the ground state, expect Jahn-Teller distortion for d3, d4, d8 and d9 . but this is rarely observed as distortions are very small For octahedral metal ion in the ground state, expect Jahn-Teller distortion for d1, d2, d4 (HS or LS), d5 (LS), d6 (HS), d7 (HS or LS) and d9 . but effects from uneven occupancy of t2g are small and rarely seen Effects are most obvious when the eg* level is unevenly occupied i.e. HS d4, LS d7 and d9
36

The Jahn-Teller Effect

Consider Cu2+ (by far the most common example)
eg* t2g

There are two ways of arranging the eg* electrons (which are antibonding and not pure d, but the result is the same)
(dz2)2(dx2-y2)1 - leads to more antibonding character on the z axis and hence elongation of bonds in that direction (dz2)1(dx2-y2)2 - leads to more antibonding character in the xy 37 plane and hence elongation of bonds in that direction

Jahn-Teller Effect
dx2-y2 dz2 dxy dxz, dyz

distortion

Net gain in CFSE (2e lowered and raised in energy) Degeneracy of eg* is lifted (state becomes single degenerate)
38

Jahn-Teller Effect
All of the cases discussed so far have had the complexes in their ground state (ie the electrons are arranged in the most stable conformation) The Jahn-Teller effect applies equally well to excited states e.g. [Ti[(H2O)6]3+Cl3, d1
purple 4000 Wave Length Angstroms green yellow orange red blue 5000 6000 7000

E2

E1

25,000

20,000

Frequency cm -1 15,000

E2 E1
39

Ground State

Exited State

Summary
Crystal Field theory: Factors that affect the magnitude of crystal field splitting Geometry Metal oxidation state The period in the transition series in which the metal occurs The spectrochemical series (strong and weak field ligands) High spin/low spin complexes Square planar vs tetrahedral geometry in d8 complexes
40

Crystal Field Theory: Uses and Limitations

It assumes purely ionic bonding The assumption that ligands are dimensionless points whereas metal orbitals have well-defined shapes is clearly inconsistent There is much evidence for covalency in TM compounds. The solution is to remove many of these invalid assumptions and allow for some covalency in the metal-ligand bond To do this we use Molecular Orbital Theory
41