Bidentate phosphine complexes of copper (I) : their syntheses and interactions with sodium tetrahydroborate and sodium cyanotrihydroborate

Abstract

Copper(l) chloride and perchlorate complexes of the types (L~L)CuCl, (L-L)[subscript 3]Cu[subscript2]X[subscript2] (X=Cl-,C10-4), C(L-L)[subscript2]Cu]C10[subscript4] (L-L=DPPM, DPPE, trans VPP, cis VPP, DPPP, DPPB,DPPPe,DPPH) have been prepared from reactions in organic solvents between the appropriate copper(II) salt and the bis phosphine in the appropriate stoichiometries. Possible arrangements of these compounds are considered on the basis of IR, [superscript 31] P NMR, [superscript1]H NMR, conductivity, and molecular weight data. All of the evidence suggests that the complexes [(L-L)[subscript2]Cu]C10[subscript4] should be formulated as ion pairs, whereas in the complexes (L-L)[subscript3]Cu[subscript2]X[subscript2] (X=Cl-, C10[subscript4 ), X is thought to be coordinated. The available evidence suggests the presence of both bridging monodentate and chelating bidentate phosphines in the (L-L)[subscript3]Cu[subscript2]X[subscript2] complexes except for L-L =trans- VPP, where all the phosphines, appear to be monodentate and bridging. The 1:1 complexes of CuCl with L-L are all formulated as dimers, [(L-L)CuCl][subscript2] with bridging chlorides, and tetrahedrally coordinated copper.