Diferrocenyltriphosphines 2. Reversible phosphine deligation in the chemistry of diferrocenyltriphosphine Ru(II) dichloride complexes with nitriles and pyridines: towards a pH-switchable catalyst?

Butler, I.R., Coles, S.J., Fontani, M., Hursthouse, M.B., Lewis, E., Malik Klma Meunier, M. and Zanello, P. (2001) Diferrocenyltriphosphines 2. Reversible phosphine deligation in the chemistry of diferrocenyltriphosphine Ru(II) dichloride complexes with nitriles and pyridines: towards a pH-switchable catalyst? Journal of Organometallic Chemistry, 637, 538-548. (doi:10.1016/S0022-328X(01)01135-4).

Abstract

The reaction of the complexes [P3-(P3fc2)RuCl2], P3fc2=[?5-(R2PC5H4)Fe-?5:?5-(C5H4P(R?)C5H4)Fe(?5-C5H4PR2)], R, R?=Ph, iPr with linear nitriles results in the formation of the pseudooctahedral complexes, e.g. [P3-(P3fc2)Ru(NCCH2R)Cl2], R=H, Ph while the reaction of [(P3fc2)RuCl2] with pyridines results in partial deligation of one of the ferrocenyl phosphine ligand arms to give the products [P2-(?5-(R2PC5H4)Fe-?5:?5-(C5H4P(R?)C5H4Fe(?5-C5H4PR2))Ru(pyr)2Cl2]. The latter products revert to the starting complexes in the absence of excess pyridine in solution. The deligated pendant phosphine may be ‘trapped’ by reaction with Pd(II) or elemental sulfur. A molecular modelling study has been carried out to verify the conformations of the products. The single crystal structures of mer-[P3-(P3fc)2Ru(CO)Cl2] and mer-[P2-(P3fc)2Ru(pyr)2Cl2] have been determined. Cyclic voltammetry supports the role assigned to pyridine in the reaction with the P3Fc2-RuCl2 complexes.

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Contributors

Author: S.J. Coles

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