SYNTHESIS, CHARACTERIZATION AND REACTIVITY OF SOME MONONUCLEAR AND DINUCLEAR CHLORORUTHENIUM COMPLEXES CONTAINING CHELATING DITERTIARY PHOSPHINES (P-P) WITH P-PRU = 1

Mixed-valence complexes of the type (P-P)ClRu(mu-Cl)3RuCl(P-P), and the [RuCl(P-P)]2(mu-Cl)2 products formed by their reduction with H2, are synthesized, where P-P is a chelating ditertiary phosphine Ph2P(CH2)nPPh2 (n = 3-6) or some related chiral analogues such as diop, chiraphos, dppcp, dpcycp, bdpp, binap, phenop or norphos (diop = Ph2PCH2CHOCMe2OCHCH2PPh2; chiraphos = Ph2PCH(Me)CH(Me)PPh2; dppcp = Ph2PCH(CH2)3CHPPh2; dpcycp = (C6H11)2PCH(CH2)3CHP(C6H11)2; bdpp(skewphos) = Ph2PCH(Me)CH2CH(Me)PPh2; binap = 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl; phenop = Ph2PN(Et)CH(CH2Ph)CH2OPPh2; norphos = Ph2PCHCHCH=CHCH(CH2)CHPPh2). The [RuCl(binap)]2(mu-Cl)2 species is also formed in solution by dissociation of PPh3 from RuCl2(binap)(PPh3) which is synthesized by phosphine exchange with RuCl2(PPh3)3. From the [RuCl(P-P)]2(mu-Cl)2 complex (P-P = Ph2P(CH2)4PPh2), a range of L(P-P)Ru(mu-Cl)3RuCl(P-P) species is readily formed, where L includes an amine, acetone, NN-dimethylacetamide, Mel, PhCN, CO, N2 or H2; the L = NEt3 adduct is made also from RUCl2(dppb)(PPh3), while the corresponding dimethyl sulfoxide adduct (L = DMSO), 17e, is synthesized directly from cis-RuCl2(DMSO)4 and the phosphine. P-31{H-1} NMR data are presented for the Ru(II) species, while characterization of 17e includes an X-ray_crystallographic analysis that confirms the trichloro-bridged formulation. Crystal data are as follows: triclinic, P1BAR, a = 12.796(1), b = 14.559(1), c = 18.429(1) angstrom, alpha = 103.983(5), beta = 99.634(6), gamma = 99.634(6)-degrees, Z = 2, R = 0.037 and R(w) = 0.046 for 9088 reflections with I greater-than-or-equal-to 3-sigma(I).