Electrochemistry of ferrocenylphosphines FcCH 2PR 2 (Fc=(η 5-C 5H 5)Fe(η 5-C 5H 4); R=Ph, CH 2OH and CH 2CH 2CN), and some phosphine oxide, phosphine sulfide, phosphonium and metal complex derivatives

Abstract

Electrochemical studies of the free ferrocenylphosphine ligands FcCH 2PR 2 (Fc=(η 5-C 5H 5)Fe(η 5-C 5H 4); R=Ph, CH 2OH and CH 2CH 2CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for P V derivatives and when the ligands are coordinated in complexes cis-PtCl 2[FcCH 2P(CH 2OH) 2], PdCl 2[FcCH 2P(CH 2OH) 2], [Au{FcCH 2P(CH 2OH) 2} 2]Cl, RuCl 2(η 6-C 10H 14)[FcCH 2P(CH 2OH) 2] and RuCl 2(η 6-C 10H 14)(FcCH 2PPh 2). The reaction pathways of the free ligands after one-electron oxidation have been examined in detail using voltammetry, NMR spectroscopy and electrospray mass spectrometry. Direct evidence for formation of a PP bonded product is presented.