Synthesis, spectroscopic characterization, and structural studies of new Cu(I) and Cu(II) complexes containing organophosphorus ligands, and crystal structures of (Ph₃P)₂Cu[S₂PMe₂], (Ph₃P)₂Cu[(OPPh₂)₂N], Cu[(OPPh₂)₂N]₂, and Cu[(OPPh₂)(SPPh₂)N]₂

Abstract

The Cu(I) complexes, (Ph 3 P) 2 CuL (L = [S 2 PMe 2 ] - , [OSPR 2 ] - (R = Me, Ph), [(XPR 2 )(YPR' 2 )N] - (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL 2 (L = [(XPR 2 )(YPR' 2 )N] - (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear NMR spectroscopy and in two cases by X-ray crystallography. (Ph 3 P) 2 Cu[S 2 PMe 2 ] (1) crystallizes in the orthorhombic space group P2 1 2 1 2 1 (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) Å, V = 3521(6) Å 3 and Z = 4, and (Ph 3 P) 2 Cu[(OPPh 2 ) 2 N] (4) in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 9.8079(2), b = 12.9141(3), c = 22.5666(5) Å, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) Å 3 and Z = 2. In both cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP 2 S 2 and CuP 2 O 2 cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh 2 ) 2 N] 2 (8) and Cu[(OPPh 2 )(SPPh 2 )N] 2 (9) crystallize in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 8.887(2), b = 10.739(2), c = 12.477(3) Å, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) Å 3 and Z = 1 for 8, and a = 9.626(2), b = 14.151(3), c = 24.752(5) Å, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) Å 3 and Z = 3 for 9. The molecule of Cu[(OPPh 2 ) 2 N] 2 (8) has a planar CuO 4 core, while in Cu[(OPPh 2 )(SPPh 2 )N] 2 (9) both planar and tetrahedral copper cores are observed in a ratio of 1:2.Key words: structure, copper, thiophosphinates, oxo- and thio-imidodiphosphinates