Complexes with sulphur and selenium donor ligands. Part II. Crystal spectra of some tris(bidentate ligand)–metal(III) complexes
- 1 January 1971
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 1409-1414
- https://doi.org/10.1039/j19710001409
Abstract
The polarised single-crystal spectra of some tris-(OO′-diethyl phosphorodithioato)- and tris(diethyldithiocarbamato)-metal(III) complexes have been recorded. All show extensive splitting of the parent terms in Oh symmetry arising from the trigonal distortions present, and the polarisation behaviour of the bands may be interpreted in terms of a D3 symmetry about the metal ion. Assignments have been made for Co3+, Cr3+, Rh3+, and Ir3+ in this symmetry. Furthermore, it is found that the A-term lies lower in energy than the E-term (both terms being derived from the parent T-term in Oh symmetry) for all the complexes examined. A point-charge calculation, with both the angle subtended at the metal by the bidentate ligands (the ‘trigonal’ angle) and also the angle of tilt of each of the ligands to the C3 axis being varied, was performed in order to rationalise this energy order. The calculation does predict this energy order for a trigonal angle of C3 axis cause little effect in the energy-level order; the order predicted for a given ‘trigonal’ angle is critically dependent on the ratio of the radial integrals, the experimental results indicating a value for the latter of 〈R2(r)〉/〈R4(r)〉 of ca. 0·9.Keywords
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