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

Diferrocenyltriphosphines 2. Reversible phosphine deligation in the chemistry of diferrocenyltriphosphine Ru(II) dichloride complexes with nitriles and pyridines: towards a pH-switchable catalyst?
Diferrocenyltriphosphines 2. Reversible phosphine deligation in the chemistry of diferrocenyltriphosphine Ru(II) dichloride complexes with nitriles and pyridines: towards a pH-switchable catalyst?
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.
ferrocene, phosphine ligand, ruthenium complexes, electrochemistry, ruthenium(ii) complexes, ligands
0022-328X
538-548
Butler, I.R.
fb76a934-e13f-4ebe-b47d-1904540fc497
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Fontani, M.
0cff908f-24b1-40af-aa12-88be4bafc9a8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Lewis, E.
6ca3b248-f4b6-4787-b93a-dddbc0b0d871
Malik Klma Meunier, M.
b249036b-a3c7-4994-9425-4c8ab1d8f4e7
Zanello, P.
80604445-a59f-444d-a95d-884963f74a74
Butler, I.R.
fb76a934-e13f-4ebe-b47d-1904540fc497
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Fontani, M.
0cff908f-24b1-40af-aa12-88be4bafc9a8
Hursthouse, M.B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Lewis, E.
6ca3b248-f4b6-4787-b93a-dddbc0b0d871
Malik Klma Meunier, M.
b249036b-a3c7-4994-9425-4c8ab1d8f4e7
Zanello, P.
80604445-a59f-444d-a95d-884963f74a74

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).

Record type: Article

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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More information

Published date: 3 December 2001
Keywords: ferrocene, phosphine ligand, ruthenium complexes, electrochemistry, ruthenium(ii) complexes, ligands

Identifiers

Local EPrints ID: 19436
URI: https://eprints.soton.ac.uk/id/eprint/19436
ISSN: 0022-328X
PURE UUID: 15e8c46e-fa09-4b65-adff-ef10540157d0
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 13 Feb 2006
Last modified: 06 Jun 2018 12:54

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