SYNTHESIS AND MULTINUCLEAR NMR STUDIES ON COPPER AND SILVER COMPLEXES OF MULTIDENTATE PHOSPHINE AND MIXED PHOSPHA/THIA LIGANDS - SINGLE CRYSTAL STRUCTURE OF [CU(P2S2)]PF6 (P2S2=PH(2)PCH(2)CH(2)SCH(2)CH(2)SCH(2)CH(2)PPH(2))

摘要

Reaction of [Cu(MeCN)(4)]PF6 or AgBF4 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. H-1, P-31 and Ag-109 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) Angstrom. The geometry at Cu-I is a severely distorted and flattened tetrahedron, with the angles at Cu-I involved in the five-membered chelate rings showing only small deviations from 90 degrees, while the unrestricted P(1)-Cu-P(2) angle is much more open at 134.88(6)degrees. The complexes [Cu(L')(2)]PF6 (L' = PhHPCH(2)CH(2)PHPh or PhHPCH(2)CH(2)CH(2)PHPh) were obtained by reaction of [Cu(MeCN)(4)]PF6 with 2 molar equiv. of the appropriate disecondary phosphine in degassed CH2Cl2. Variable-temperature P-31 and Cu-63 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. [References: 27]