Israel Journal of Chemistry · 1976 · 18 citations · 9 references
Natural SciencesChemistryElectrochemistryInorganic ChemistryOrganic ChemistryCoordination ChemistryHeterocyclic ChemistryMetal-ligand BondingTransition Metal ChemistryTransition Metal ComplexesBondingElectrochemical OxidationLigand Effects On ReactivityManganese ChemistryManganese Redox ChemistryStereospecific Reactions
Abstract The reactions of Mn(CO) 5‐n (CNMe) n Br (n = 2, 3, 4) with either CO or CNMe in the presence of a halide acceptor are found to be stereospecific, with incoming ligand replacing the halide ion. These reactions were used in the syntheses of mer ‐ and fac ‐[Mn(CO) 3 (CNMe) 3 ]PF 6 and cis ‐ and trans ‐[Mn(CO) 2 (CNMe) 4 ]PF 6 . A cyclic voltammetric study showed that the isomeric complexes had different E 1/2 values. The difference in eases of oxidation was rationalized qualitatively based on the abilities of CO and CNMe to serve as π acceptors. This suggestion was supported quantitatively by theoretical calculations which defined the degree of stabilization of the HOMO levels in these complexes through π bonding.
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