Synthesis and X-ray structures of RuCpClL [L = (eta(1)-PPh(2)py)(2) and eta(2)-triphos] and [RuCp{eta(3)- (PPh2)(3)CH}][PF6]. The first eta(3)-(PPh2)(3)CH complex of Ru(II)

Diphenyl-2-phosphinopyridyl (dppy) and 1,1,1 -tris(diphenylphosphinomethyl) ethane (triphos) react with RuCpCl(COD), (COD = cycloocta-1,5-diene; Cp = e ta (5)-C5H5 by the displacement of the COD ligand to give, respectively, Ru CpCl(eta (1)-dppy)(2) (I) and RuCpCl(eta (2)-triphos) (II). When RuCpCl(PPh 3)(2) was used as the starting material, substitution of PPh3 ligands by dp py ligands afforded a mixture of di- (I) and mono-substituted RuCpCl(dppy)( PPh3) (III) complexes. The structure of (I) has been determined by X-ray cr ystallography and has been refined to a final R value of 0.0516. Both dppy ligands are P-coordinated. Crystal structure analysis of (II) shows that tw o phosphorus atoms are coordinated to the ruthenium atom in a chelating mod e, and that the third phosphorus atom is free. This structure was refined s uccessfully to a conventional R value of 0.0495. Reaction of RuCpCl(eta (2) -tripod) {tripod = 1,1,1-tris(triphenylphosphino)methane} with an excess of NH4PF6 gives the first eta (3)-tripod ruthenium complex [RuCp(eta (3)-trip od)][PF6] (IV) in 94% yield. The analogous triflate complex [RuCp(eta (3)-t ripod)][CF3SO3] (IV) has also been prepared. Crystal structure analysis of complex (IV) shows that all three phosphorus atoms are coordinated to the r uthenium atom, and that all three P-C-P angles are less than 90 degrees, le ading to considerable strain in the tricyclic system. The structure was ref ined successfully to a conventional R value of 0.0538. Treatment of the tri flate complex CV) with [(C4H9)][Rh(CO)(2)Cl] gave the known complex CpRu(mu -CO)(2)(mu -Ph2PCH2PPh2)RhCl2 via a P-C bond cleavage reaction. (C) 2001 P ublished by Elsevier Science B.V.