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The Electronic Spectra of Coordination Compounds

[V(H2O)6]2+

[V(H2O)6]3+

[Cr(NH3)6]3+

[Cr(NH3)5Cl]2+

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. Electronelectron 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 spin-forbidden, and have a very low intensity.

Qualitative Explanation
Consider a Cr(III) complex such as [Cr(NH3)6]3+. The ground state configuration is: ____ ____ A transition from the dz2 dx2-y2 dxy to the dx2-y2, or the dyz or dxz to the dz2 ____ ____ ____ orbitals involve a relatively dxy dyz dxz minor change in environment.

Qualitative Explanation
The transition from the dxz orbitals to the dz2 orbitals involves a relatively minor change in the electronic environment.

Qualitative Explanation
Consider a Cr(III) complex such as [Cr(NH3)6]3+. The ground state configuration is: ____ ____ A transition from the dz2 dx2-y2 dxy to the dz2, or the dyz or dxz to the dx2-y2 ____ ____ ____ orbitals involve a major dxy dyz dxz change in environment.

Qualitative Explanation
The transition from orbitals in the xy plane to the dz2 orbitals involves a fairly major change in the electronic environment.

Qualitative Explanation
Since the promotion of an electron from the t2g set of orbitals to the eg set can involve differing changes in environment, several peaks will be seen in the spectrum.

3d Multi-electron Complexes
For complexes with more than one electron in the 3d (and 4s) orbitals of the metal, electron interactions must be considered. The electrons are not independent of each other, and the orbital angular momenta (ml values) and the spin angular momenta (ms values) interact.

4d and 5d Metal Complexes


The lower transition metals undergo further coupling (called j-j coupling or spin-orbit coupling).

3d Multi-electron Complexes
The interaction is called Russel-Saunders or L-S coupling. The interactions produce atomic states called microstates that are described by a new set of quantum numbers. ML = total orbital angular momentum =ml MS = total spin angular momentum = ms

More Complex Electronic Processes

Fluorescence: absorption of radiation to an excited state, followed by emission of radiation to a lower state of the same multiplicity Phosphorescence: absorption of radiation to an excited state, followed by emission of radiation to a lower state of different multiplicity Singlet state: spins are paired, no net angular momentum (and no net magnetic field) Triplet state: spins are unpaired, net angular momentum (and net magnetic field)

S=5/2

S=5/2

S=1/2

dx2-y2 dz 2

dx2-y2

dxy dxz,dyz
dxy

dxy dxz,dyz

dx2-y2 dz2 Tetrahedral


2 OH2 OH2

dz 2 dxz,dyz Square Planar


22-

Octahedral

H2O H2O

OH2 Ni

Cl Ni Cl

Cl Cl

N C Ni C N C C

H2O Octahedral Coordination number =6

Tetrahedral (CN=4)

Square Planar (CN=4)

Ni(II) d8 S = 1

Ni(II) d8 S =1

Ni(II) d8 S = 0

Distribution of high- and low-spin complexes of the d-block metal ions:


Co(III) is big exception all low-spin except for [CoF6]31st row tend to be high-spin except for CN- complexes

2nd and 3rd row are all low-spin except for PdF2 and [PdF6]4-