Unexpected reactivity of PdCl(2) and PtCl(2) complexes of the unsaturated diphosphine o-Me(2)TTF(PPh(2))(2) toward chloride abstraction with thallium triflate

Thomas Devic; Patrick Batail; Marc Fourmigué; Narcis Avarvari

doi:10.1021/ic035447y

Unexpected reactivity of PdCl(2) and PtCl(2) complexes of the unsaturated diphosphine o-Me(2)TTF(PPh(2))(2) toward chloride abstraction with thallium triflate

Inorg Chem. 2004 May 17;43(10):3136-41. doi: 10.1021/ic035447y.

Authors

Thomas Devic¹, Patrick Batail, Marc Fourmigué, Narcis Avarvari

Affiliation

¹ Laboratoire "Chimie Ingénierie Moléculaire et Matériaux" (CIMMA), UMR 6200 CNRS-Université d'Angers, Bât. K, UFR Sciences, 2 bd Lavoisier, 49045 Angers, France.

PMID: 15132619
DOI: 10.1021/ic035447y

Abstract

Attempted thallium triflate abstraction of chloride anions from the MCl(2) complexes of the unsaturated chelating diphosphines o-dimethyl-bis(diphenylphosphino)tetrathiafulvalene (P2) (M = Pd, Pt) and cis-1,2-bis(diphenylphosphino)ethylene (dppen) (M = Pd) affords, surprisingly, a Tl(OTf) adduct in the case of (P2)PdCl(2) and (P2)PtCl(2), with no chloride abstraction, and a dicationic bis(palladium) bis(triflate) salt in the case of (cis-dppen)PdCl(2), in which only one Cl anion was removed. The crystal structures of these complexes were determined by X-ray analysis, which established the formulations (P2)MCl(2).Tl(OTf) (M = Pd, Pt) and [(dppen)PdCl](2)(OTf)(2), respectively. These compounds can be seen as possible intermediates in the general chloride abstraction process between (P-P)MCl(2) (M = Pd, Pt) and thallium triflate.