Kinetic and electrochemical study of nitrile adducts of tetrachloro-bis (1,2-bis(diphenylphosphine)methane)dirhenium(II)

Abstract

The addition of two nitrile ligands to the complex Re2Cl4-(dppm)2 (dppm= 1,2-bis(diphenylphosphine)methane)in CH2Cl2 solution has been investigated electrochemically. Upon addition of one equivalent of nitrile NCR (R = aromatic or aliphatic group) to the CH2Cl2/0.1mtetra-N-butylammonium hexafluorophosphate (TBAH) solution, Re2Cl4(dppm)2(NCR) is formed immediately, without dissociation of chloride; electrochemical investigation indicates this nitrile addition is reversible upon oxidation of the dirhenium complex. On addition of two or more equivalents of nitrile, a slow ligand substitution takes place with addition of a second nitrile and concomitant loss of a chloride ion to form [Re2Cl3-(dppm)2(NCR)2]+. The rate of addition of nitrile to Re2Cl4(dppm)2(NCR) appears to depend on the electrondonating or electron-withdrawing abilities of the ligand. The change from monoadduct to diadduct was followed with differential pulse voltammetry for various concentrations of added nitrile. The addition was found to be first order in nitrile.