MCD spectra of OsI62-and the trans-mixed hexahalo complexes of Ir4+and Os4+
- 1 November 1975
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 30 (5), 1569-1588
- https://doi.org/10.1080/00268977500103081
Abstract
The absorption and magnetic circular dichroism (MCD) spectra of the n-tetrabutylammonium salts of OsI6 2- and trans-IrCl4Br2 2-, OsCl4Br2 2- and OsBr4Cl2 2- and of the trans-tetraethylammonium salts of IrBr4Cl2 2-, OsCl4I2 2-, and OsI4Cl2 2- were measured in KBr pellets at liquid helium temperature. The bands in the absorption spectra, which are very similar for analogous Ir4+ and Os4+ mixed halides, are assigned with the help of MCD data to ligand-to-metal charge-transfer transitions using the j-j model previously found successful in interpreting the OsCl6 2- and OsBr6 2- spectra. The signs and, where possible, the magnitudes of the tetragonal distortion parameters are estimated for these mixed halides by fitting the spectra, and the signs are compared with those predicted by simple molecular orbital arguments. The principal bands of OsI6 2- are assigned to charge-transfer transitions which correspond to the analogous ones in OsBr6 2- and OsCl6 2-. The importance of second-order ligand spin-orbit coupling is demonstrated.Keywords
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