C-H and P-C(Ph) activation competitive processes caused by interaction with the solvate [cis-Pt(C6F5)2(thf)2

The study of the reaction between the ethylene Pt(eta-H2C = CH2)(PPh3)2] or alkyne Pt(eta2-HC triple bond] CR)(PPh3)2] (R = SiMe3 1, Bu(t) 2) complexes with cis-Pt(C6F5)2(thf)2] (thf = tetrahydrofuran) has enabled us to observe the existence of competitive processes between the activation of a P-C(Ph) bond on the PPh3 ligand, to give the binuclear derivative cis-(C6F5)2Pt(mu-Ph)(mu-PPh2)Pt(PPh3)] 3, and the activation of a C-H bond of the unsaturated group, to give the corresponding (mu-hydride)(mu-vinyl) cis, cis-(PPh3)2Pt(mu-H)(mu-1kappaC(alpha):eta2-CH = CH2)Pt(C6F5)2] 4 or (mu-hydride)(mu-alkynyl) cis,cis-(PPh3)2Pt(mu-H)(mu-1kappaC(alpha):eta2-C triple bond]CR)Pt(C6F5)2] (R = SiMe3 5, Bu(t) 6) compounds, respectively. The monitoring of these reactions by NMR spectroscopy has allowed us to detect several intermediates, and to propose a mechanism for the C-H bond activation. In addition, the structures of the (muo-hydride)(mu-alkynyl) complex 5 and the unprecedented (mu-hydride)(mu-vinyl) derivative 4 have been obtained by X-ray crystallographic analyses.