Phenyl complexes of ruthenium(II): competition between carbonyl substitution and formation of benzoyl complexes, and an X-ray study of a benzoyl complex

Abstract

Complexes [Ru(CO)₂(C₆H₄X-4)Y(PMe₂Ph)₂](X = H, Y = Cl, l, or O₂CMe; X = OMe, Cl, or NMe₂, Y = Cl) react with Me₃CNC in CHCl₃ solution to yield carbonyl substitution products [Ru(CO)(CNCMe₃)(C₆H₄X-4)Y(PMe₂Ph)₂] and benzoyl complexes [Ru(CO)(CNCMe₃)₂-(COC₆H₄X-4)(PMe₂Ph)₂]⁺ in proportions which vary widely according to the conditions used and the nature of X and Y. The most probable route to the benzoyl complexes appears to be via intermediates of formula [Ru(CO)(CNCMe₃)(COC₆H₄X-4)Y( PMe₂Ph)₂]. The structure of [Ru(CO)(CNCMe₃)₂(COPh)(PMe₂Ph)₂]I₃ has been determined by X-ray crystallography.