Nucleophilicites of the metal carbonyl anions: Effects of ligands, solvent, and countercation

The effects of ligand environment, solvent, and countercation on the nucleophilicity of metal carbonyl anions have been measured. The reactions of the metal carbonyl anion with MeI were measured by infrared stopped-flow spectrometry. The nucleophilicity was found to be relatively unaffected by changes in solvent. Also, a rather small effect of the countercation was observed with a slower rate for the more interacting cation. The rate of reaction of the ligands with MeI was found to directly parallel the donor capability of the ligand. The oxidation potentials of the anions were also measured and are reported. 11 refs., 1 fig., 3 tabs.