Spectra of coordination compounds

Kettle, S. F. A. (1969). Coordination Chemistry. Appleton, Century Crofts, New York. A good introduction to interpreting spectra of coordination compounds is given. 

In later chapters, symmetry will be a valuable tool in the construction of molecular orbitals (Chapters 5 and 10) and in the interpretation of electronic spectra of coordination compounds (Chapter 11) and vibrational spectra of organometallic compounds (Chapter 13). 

Free-ion terms are very important in the interpretation of the spectra of coordination compounds. The following examples show how to determine the values of L, Mi, S, and Ms for a given term and how to prepare microstate tables from them. 

Spin-oibit coupling can have significant effects on the electronic spectra of coordinations compounds, especially those involving fairly heavy metals (atomic number >40). 

In the interpretation of spectra of coordination compounds, it is often important to identify the lowest-energy term. A quick and fairly simple way to do this is given here, using as an example a d configuration in octahedral symmetry. 

Electronic Spectra of Coordination Compounds 391 n-3-2 CORRELATION DIAGRAMS... 

Absorption spectra of coordination compounds can be used to determine the magnitude of the ligand field splitting, which is A for octahedral complexes. It should be made clear from the outset that the accuracy with which Ag can be determined is to some extent limited by the mathematical tools used to solve the problem. Absorption spectra often have overlapping bands to determine the positions of the bands accurately, therefore, requires an propriate mathematical technique for reducing overlapping bands into their individual components. Such analysis is beyond the scope of this text. However, we can often obtain A values (and sometimes values of the Racah parameter, B) of reasonable accuracy simply by using the positions of the absorption maxima taken directly from the spectra. 

Nakamoto K (1997) Infrared and Raman spectra of coordination compounds, 5th edn. Wiley, New York... 

Mizuoka and Ikeda [378] observed that the V3 of the (U 02) ion at 895 cm in DMSO (dimethyl sulfoxide) solution is shifted to 770 cm when reduced electro-chemically to the (U 02) ion. Vibrational spectra of coordination compounds containing dioxo(0=M=0) groups are discussed in Chapter 3 (in Part B). 

Table ll-2e lists the vibrational frequencies of linear XYZ-typc molecules. Some of these vibrations split into two because of Fermi resonance or the crystal-held effect. Vibrational spectra of coordination compounds containing pseudohalide ions such as NCS, NCO", and NJ are discussed in Sec. Ill-15. 

The vibrational spectra of coordination compounds containing pseudohalogeno groups were discussed in Sec. 111-15. The vibrational spectra of azido complexes have been reported for CHjZnNj," CH3HgN3, "... 

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