Electrochemistry of ferrocenylphosphines FcCH2PR2 (Fc = (η5-C5H5)Fe(η5-C5H4);: R = Ph, CH2OH and CH2CH2CN), and some phosphine oxide, phosphine sulfide, phosphonium and metal complex derivatives

Electrochemical studies of the free ferrocenylphosphine ligands FcCH(2)PR(2) (Fc = (eta(5)-C5H5)Fe(eta(5)-C5H4); R = Ph, CH2OH and CH2CH2CN) 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-PtCl2[FcCH(2)P(CH2OH)(2)], PdCl2[FcCH(2)P(CH2OH)(2)], [Au{FcCH(2)P(CH2OH)(2)}(2)]Cl, RuCl2(eta(6)-C10H14)[FcCH(2)P(CH2OH)(2)] and RuCl2(eta(6)-C10H14)(FcCH(2)PPh(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. (C) 2003 Elsevier Science B.V. All rights reserved.