A Trigonal Planar μ3-Fluorido Coinage Metal Complex from a Dicationic (Diphosphinomethane)copper(I) Dimer:  Syntheses, Structures, and Bonding‡

Abstract

The triflate and hexafluorophosphate salts of [Cu2(mu-dtbpm)2]2+ (1(2+)) [dtbpm = bis(di-tert-butylphosphino)methane, tBu2PCH2PtBu2] and of [Cu3(mu 3-F)(mu-dtbpm)3]2+ (2(2+)) were synthesized and characterized. Coordination of solvent or counterions to 1(2+) is observed neither in solution nor in the solid state. The two copper(I) centers in 1(2+) indicate weak d10-d10 closed-shell interactions. 1(2+) reacts slowly with PF6- anions in acetone or KF in CH2Cl2 to yield the mu 3-fluorido complex 2(2+) with idealized D3 symmetry, containing a trigonal planar Cu3F core, as shown by single-crystal X-ray diffraction. Distinct structural differences are observed compared to monocationic bicapped, trinuclear copper(I) dppm halide complexes [dppm = bis(diphenylphosphino)methane, Ph2PCH2PPh2]. The average Cu-Cu, Cu-F, and Cu-P distances and the P-Cu-P' angle in 2(2+) are 3.85, 2.22, and 2.28 A and 144.3 degrees, respectively. The P2Cu units are twisted out of the Cu3F plane by an average angle of 18.4 degrees. DFT calculations (BPW91/LANL2DZ) for the model [Cu3(mu 3-F)(mu-dhpm)3]2+ (dhpm = diphosphinomethane, H2PCH2PH2) are used to explain the formation, structure, and bonding pattern of 2(2+).