The reduction and oxidation of cationic carbonyl complexes of manganese with phosphoniodithioformate: X-ray crystal structure of [Mn(CO) 4(S 2CPCy 3)]ClO 4

Abstract

Manganese carbonyl complexes of the types behaviour have been studied by cyclic voltammetry and controlled potential electrolysis, showing that they undergo one-electron reduction and one-electron oxidation at potentials that depend mainly on the number of carbonyls. The results have been explained on the basis on an MO study at an EH level carried out on the model complexes [Mn(CO) 4(S 2CPH 3)] + ( 1b), fac-[Mn(CO) 3PH 3(S 2CPH 3)] + ( 2d), cis,trans-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 3d), mer-[Mn(CO) 3PH 3(S 2CPH 3)] + ( 4), trans,cis-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 5), and cis,cis-[Mn(CO) 2(PH 3) 2(S 2CPH 3)] + ( 6).