Ruthenium Arene Derivatives of Chiral Ferrocene-Based P,N or P,O Ligands. Transformation of Chloro–Alcohol into Hydrido–Carbonyl Complexes

Abstract

Several ferrocene-based chiral nonracemic aminophosphine and racemic hydroxyphosphine ligands have been used in the synthesis of RuII(arene) derivatives (arene = p-cymene, benzene). The reaction of suitable ruthenium complexes with the aminophosphine (P,N) ligands and NaBPh4 led to chelate complexes [RuCl(arene)(P,N)]BPh4 in which the ferrocenyl ligand is coordinated in a bidentate fashion. When these reactions were carried out with the hydroxyphosphine (P,O) ligands the alcohol functionality was oxidized, and hydrido–ketone (or hydrido–aldehyde) derivatives of the type [RuH(arene)(PC═O)]BPh4 were obtained. The structures of two derivatives containing either an aminophosphine or a ketophosphine ligand were determined by X-ray diffraction. The reaction of the hydroxyphosphine ligands with the ruthenium precursors was studied in detail. Derivatives with coordinated hydroxyphosphine ligands were isolated and, in the case of a p-cymene hydroxyphosphine derivative, the rate constants and also the thermal and t...