The Electronic Spectra of Coordination Compounds

Introduction
Many transition metal complexes are colored. This is due to transitions of electrons between the molecular orbitals that are formed largely by the d orbitals on the metal. Many transitions are in the visible range, with the color of the complex taking on the complementary color of the frequency or frequencies absorbed.

Introduction

General Features
Absorption bands in electronic spectra are usually broad, and occur much more rapidly than molecular vibrations. As a result, the spectra represent a snapshot of molecules in various vibrational and rotational states.

General Features
Extinction coefficients will range from <1 up to 50,000 M-1cm-1 depending upon the type of electronic transition and whether it is permitted based on selection rules.

Selection Rules
Electronic transitions obey the following selection rules: 1. S = 0. Electrons cannot change spin. 2. The Laporte rule states that there must be a change in parity. Only gu or ug transitions are allowed. Thus, all dd transitions are forbidden by this selection rule.

The UV/Vis spectra of transition metal complexes shows the transitions of the electrons. Analysis of these spectra can be quite complex.

Electron Spectra
The UV/Vis spectra are used to determine the value of o for the complex. The spectra arise from electronic transitions between the t2g and eg sets of molecular orbitals. Electron-electron interactions can greatly complicate the spectra. Only in the case of a single electron is interpretation of the spectrum straightforward.

Obtaining o
For a d1 configuration, only a single peak is seen. It results from the electron promotion from the t2g orbitals to the eg orbitals. The toothed appearance of the peak is due to a Jahn-Teller distortion of the excited state. The energy of the peak = o.

General Observations
d1, d4, d6 and d9 usually have 1 absorption, though a side hump results from Jahn-Teller distortions.

General Observations
d2, d3, d7 and d8 usually have 3 absorptions, one is often obscured by a charge transfer band.

General Observations
d5 complexes consist of very weak, relatively sharp transitions which are spinforbidden, and have a very low intensity.

Lecture 18. d-d spectra and MO theory:

UV visible infrared
3A 2g

3T2g

3A 2g

1Eg

[Ni(NH3)6]2+

, cm-1

The electronic spectra of d-block complexes:

The features of electronic spectra that we need to be able to master are: 1) naming of electronic states and d-d transitions, e.g.3A2g, or 3A2g1Eg 2) Explanation of relative intensities of bands in the spectra of complexes of d-block metal ions. (The Laporte and spin selection rules) 3) calculation of the crystal field splitting parameters from energies of d-d bands

Naming of electronic states:

In names of electronic states, e.g. 4A2g, the labels A, E, and T, stand for non-degenerate, doubly degenerate, and triply degenerate, while the numeric superscript stands for the multiplicity of the state, which is the number of unpaired electrons plus one. Note that the electronic states can be ground states (states of lowest energy) or excited states: energy
g = gerade

eg
Non-degenerate ground state =

4A
Multiplicity = 3 unpaired electrons + 1 =4

2g
t2g

Naming of electronic states (contd.):

NOTE: In determining degeneracy, one can re-arrange the electrons, but the number of unpaired electrons must stay the same, and the number of electrons in each of the eg and t2g levels must stay the same. Non-degenerate energy triply degenerate non-degenerate

eg

eg

eg

t2g
6A 2g 3T 2g

t2g
1A 2g

t2g
Multiplicity =0+1

Multiplicity =5+1

Multiplicity =2+1

Naming of electronic states (contd.):

ground state excited state ground state

eg
5E g 5T 2g

eg
2E g

eg

t2g
energy
3A 2g

t2g eg
1E g 3T 2g

t2g eg

eg

t2g
ground state excited state

t2g
excited state

t2g

Electronic transitions:
eg
3A 2g

eg
3A 2g

3T2g

3T 2g

t2g eg
3A 2g

t2g
3A 2g

1Eg

eg
1E g

ground state

t2g

excited state

t2g

The electronic spectrum of [Ni(H2O)6]2+:

The complex looks green, because it absorbs only weakly at 500 nm, the wavelength of green light.

UV

visible
1Eg

infrared [Ni(H2O)6]2+

3A 2g

green

3A 2g

3T2g

The electronic spectrum of [Ni(H2O)6]2+:

On the previous slide we saw the two bands due to the 3A 3T 3A 1E transitions. The band at = and 2g 2g 2g g 1180 nm which is the 3A2g 3T2g transition shown below, corresponds to for the complex. This is usually expressed as in cm-1 = (1/(nm)) x 107 = 8500 cm-1.

eg
3A 2g

eg
3A 2g

3T2g

3T 2g

t2g

= = 8500 cm-1

t2g

The electronic spectrum of [Ni(H2O)6]2+:

Note the weak band at 620 nm that corresponds to the 3A 1 2g Eg transition. The electron that is excited moves within the eg level, so that the energy does not involve , but depends on the value of P, the spin-pairing energy. The point of interest is why this band is so weak, as discussed on the next slide.

eg
3A 2g

eg
3A 2g

1Eg

1E g

t2g

= 16100 cm-1

t2g

The electronic spectrum of [Ni(H2O)6]2+:

The two peaks at higher energy resemble the 3A2g3T2g transition, but involve differences in magnetic quantum numbers of the d-orbitals, and are labeled as 3A2g3T1g(F) and 3A2g3T1g(P) to reflect this:
3A 2g

3T1g(P)

[Ni(H2O)6]2+
3A 2g 3A 2g

3T1g(F)

3A 2g

3T2g

1Eg

The Selection rules for electronic transitions

There are three levels of intensity of the bands that we observe in the spectra of complexes of metal ions. These are governed by two selection rules, the Laporte selection rule, and the spin selection rule. The Laporte selection rule reflects the fact that for light to interact with a molecule and be absorbed, there should be a change in dipole moment. When a transition is forbidden, it means that the transition does not lead to a change in dipole moment.

The Laporte Selection rule: This states that transitions where there is no change in parity are forbidden:

gg uu
forbidden

gu ug
allowed

The Selection rules for electronic transitions

All transitions within the d-shell, such as 3A2g3T2g are Laporte forbidden, because they are gg. Thus, the intensity of the d-d transitions that give d-block metal ions their colors are not very intense. Charge transfer bands frequently involve pd or dp transitions, and so are Laporte-allowed and therefore very intense. The Spin Selection rule: This states that transitions that involve a change in multiplicity (or number of unpaired electrons) are forbidden. This accounts for why transitions within the d-shell such as 3A2g1Eg that involve a change of multiplicity are much weaker than those such as 3A2g3T2g that do not.

The Selection rules for electronic transitions

Charge-transfer band Laporte and spin allowed very intense
3A 2g

1Eg Laporte and spin forbidden very weak

a, b, and c, Laporte forbidden, spin allowed, intermediate intensity b c

[Ni(H2O)6]2+

3A 2g

3T2g

The Intensity of bands in complexes of d-block ions: The three types of bands present in e.g. [Ni(H2O)6]2+ are: 1) Laporte-allowed plus spin allowed charge transfer bands of very high intensity

2) Laporte-forbidden plus spin-allowed dd transitions (e.g. 3A2g3T2g) of moderate intensity

3) Laporte forbidden plus spin-forbidden dd transitions (3A2g1Eg) of very low intensity.

The MO view of electronic transitions in an octahedral complex

t2gt1u* ML Charge transfer Laporte and spin allowed
4p 4s eg* t2g 3d

t1u* a1g*

t2geg dd transition Laporte forbidden Spin-allowed or forbidden

The eg level in CFT is an eg* in MO

-donor orbitals of six ligands t1ut2g LM Charge transfer Laporte and spin allowed

In CFT we consider only the eg and t2g levels, which are a portion of the overall MO diagram

eg a1g t1u

Why do we see forbidden transitions at all?

There are two mechanisms that allow forbidden electronic transitions to become somewhat allowed. These are: 1) Mixing of states: The states in a complex are never pure, and so some of the symmetry properties of neighboring states become mixed into those of the states involved in a forbidden transition.

2) Vibronic Coupling: Electronic states are always coupled to vibrational states. The vibrational states may be of opposite parity to the electronic states, and so help overcome the Laporte selection rule.

Mixing of states: Comparison of [Ni(H2O)6]2+ and [Ni(en)3]2+:

The spin-forbidden 3A2g 1Eg is close to the spin-allowed 3A 3 2g T2g(F) and borrows intensity by mixing of states
Note: The two spectra are drawn on the same graph for ease of comparison.

The spin-forbidden 3A2g 1Eg is not close to any spin allowed band and is very weak
1Eg 3T

3A 2g

3A 2g

2g(F)

[Ni(H2O)6]2+ [Ni(en)3]2+
3A 2g

3T2g

Vibronic coupling:
Electronic transitions are coupled to vibrations of various symmetries, and the latter may impart opposite parity to an electronic state and so help overcome the Laporte selection rule: Electronic transitions, as seen energy in the spectra of complexes of coupled vibration 5 Ni(II) shown above, are always is u 4 3 very broad because they are 1 electronic excited coupled to vibrations. The state is g transitions are thus from ground g(g+u) transition states plus several vibrational is allowed states to excited states plus 5 gg transition several vibrational states (1, 2, 3), 3 is forbidden 1 so the electronic band is actually electronic ground a composite of electronic plus state is g vibrational transitions.

Symmetry of vibrational states, and their coupling to electronic states:

observed spectrum E + 1 E + 2 E + 3 E E- 1 E- 2 E- 3

A1g symmetry vibration

T1u symmetry vibration

(symbols have same meaning for vibrations: A = non-degenerate, T = triply degenerate, g = gerade, u = ungerade, etc.)

The band one sees in the UV-visible spectrum is the sum of bands due to transitions to coupled electronic (E) and vibrational energy levels (1, 2, 3)

The spectra of high-spin d5 ions:

For high-spin d5 ions all possible d-d transitions are spin-forbidden. As a result, the bands in spectra of high-spin complexes of Mn(II) and Fe(III) are very weak, and the compounds are nearly colorless. Below is shown a d-d transition for a high-spin d5 ion, showing that it is spin-forbidden.

energy

eg
6A 2g

eg
4T2g

t2g

t2g

Complexes of Gd(III) are colorless, while those of other lanthanide M(III) ions are colored, except for La(III) and Lu(III). Why is this?

The spectra of complexes of tetrahedral metal ions:

As we have seen, a tetrahedron has no center of symmetry, and so orbitals in such symmetry cannot be gerade. Hence the d-levels in a tetrahedral complex are e and t2, with no g for gerade. This largely overcomes the Laporte selection rules, so that tetrahedral complexes tend to be very intense in color. Thus, we see that dissolving CoCl2 in water produces a pale pink solution of [Co(H2O)6]2+, but in alcohol tetrahedral [CoCl2(CH3CH2OH)2] forms, which is a very intense blue color. This remarkable difference in the spectra of octahedral and tetrahedral complexes is seen on the next slide:

The spectra of octahedral [Co(H2O)6]2+ and tetrahedral [CoCl4]2- ions:

[CoCl4]2The spectra at left show the very intense d-d bands in the blue tetrahedral complex [CoCl4]2-, as compared with the much weaker band in the pink octahedral complex [Co(H2O)6]2+. This difference arises because the Td complex has no center of symmetry, helping to overcome the gg Laporte selection rule.

[Co(H2O)6]2+