Ruthenium complexes containing Group 5B donor ligands. Part 8. Reactions of binuclear carbonyl- and thiocarbonyl-ruthenium(II) triphenylphosphine complexes with alkoxy(phenyl)phosphines and of mononuclear ruthenium(II) alkoxy(phenyl)phosphine complexes with carbon monoxide

Abstract

Reaction of [Ru₂(Y)Cl₄(PPh₃)₄](Y = CO or CS) with excess of L in benzene leads to ready bridge cleavage and ligand exchange to give mixtures of [Ru(Y)Cl₂L₃] and [RuCl₂L_n][L = PPh₂(OR)(R = Me or Et) or PPh(OMe)₂; n= 3 or 4]. These monosubstituted carbonyl and thiocarbonyl complexes can also be synthesized by carbonylation of [RuCl₂L_n] and by reaction of [{Ru(CS) Cl₂(PPh₃)₂}₂] with excess of L respectively. In alcohols [Ru(Y)Cl₂{PPh₂(OR)}₃] rearrange to [Ru(Y)Cl{PPh₂(OMe)}₃]⁺ and [{Ru(Y)Cl[PPh₂(OEt)]₃}₂]²⁺ respectively, whereas [Ru(Y)Cl₂{PPh(OMe)₂}₃] is recovered unchanged. Structures are assigned to these complexes mainly on the basis of ¹H and ³¹P-{¹H} n.m.r. studies.