Synthesis and multinuclear NMR studies on copper and silver complexes ofmultidentate phosphine and mixed phospha/thia ligands. Single crystal s tructure of [Cu(P2S2)]PF6 (P2S2=Ph2PCH2CH2SCH2CH2PPh2)

Article abstract of DOI:10.1016/0277-5387(95)00042-Q

Reaction of [Cu(MeCN)4]PF6 with 1 molar equiv. of L (L=tetraphos-1, P2S2) in degassed acetone followed by addition of diethyl ether yielded the complexes of stoichiometry [M(L)](+)X(-), M=Cu, X(-)=PF6(-); M=Ag, X(-)=BF4(-), in high yield. (1)H, (31)P and (109)Ag NMR spectroscopic data consistent with this formulation are presented. The complex Cu(L)PF6 contains discrete [Cu(P2S2)](+) cations and PF6(-) anions. The Cu(I) ion is tetra-ligated to the P2S2 ligand via both the P- and S-donor atoms, Cu-S=2.385(2), 2.367(2), Cu-P=2.233(2), 2.242(2) ?. The geometry at Cu(I)is a severely distorted and flattened tetrahedron, with the angles at C u(I) involved in the five-membered chelate rings showing only small deviations from 90°, while the unrestricted P(1)-Cu-P(2) angle is much more open at 134.88(6)°. The complexes [Cu(L')2]PF6 (L'=PhHPCH2CH2PHPh or PhHPCH2CH2CH2PHPh) were obtained by reaction of [Cu(MeCN)4]PF6 with 2 molar equiv. of the appropriate disecondary phosphine in degassed CH2Cl2. Variable-temperature (31)P and (63)Cu NMR spectroscopic studies confirmed the 1:2 Cu:L' stoichiometry and indicated an approximately tetrahedral arrangement of the four P donors around the Cu(I) ion in each case.