Abstract
The 193Ir Mössbauer isomer shifts of a set of closely related iridium carbonyl chloride complexes with oxidation states +1, +1.1, +1.4, and +2 have been found to decrease with increasing oxidation state. This is the inverse of the normal trend due to decreased shielding of the s electrons from the nuclear charge by removal of d electrons, and is attributed to the combined effect of strong π-backbonding and 6s character in the nominally 5d electrons removed in changing the oxidation state. An inverted isomer shift-oxidation state dependence is predicted for d m ( m > 7) metal complexes with strong π-acceptor ligands.
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