Chemistry of Heterobifunctional Diazaphospholylphosphines. 4. Complexation and Reduction Reactions of Platinum(II) and Palladium(II) with Phosphine-Substituted (Fluoro, Dimethylamino, Trifluoroethoxy) 4-Phosphino-2,5-dimethyl-2H-1,2,3σ2-diazaphospholes. Structure of a Novel Platinum(0) Tetrakis(difluorophosphine) Complex

Abstract

Selected platinum(II) and palladium(II) complexes react with 4-(difluorophosphino)-2,5-dimethyl-2H-1,2,3σ2-diazaphosphole (LF) to form the expected X2M(LF)2 complexes. In some cases, redox processes yield stable, solid, M0(LF)4 complexes; thus Pd(cod)Cl2 with LF gave a mixture of the Pd0 and PdII complexes whereas Pt(cod)Cl2 gave only the Pt(LF)2Cl2 complex. With limited LF, (cod)Pt(Me)Cl gave the expected (LF)2Pt(Me)Cl complex, but when the reaction was carried out with excess LF, PtII was reduced to Pt0 to form the Pt0(LF)4 complex. This complex was structurally characterized. Crystal data for C16H28F8N8O2P8Pt: tetragonal, I42m (No. 121), a = 11.961(2) A, c = 15.034(3) A, V = 2150.8(6) A3, Z = 2. Final indices: GOF = 1.299 [Fo2 ≥ −3σ(Fo2)] and R1 = 0.0381, wR2 = 0.1180 (for Fo2 > 2σ(Fo2)) and R1 = 0.0395, wR2 = 0.1188 for all data. The structure around the Pt0 atom was revealed as a slightly squashed tetrahedron surrounded by four phospholylphosphine ligands coordinated through the exocyclic phosphine...