Structural and Solid-State ³¹P N.M.R. Studies on a Novel Fluorotris(triphenyl-phosphine)copper(I) Adduct

Abstract

The synthesis of the title compound as its triphenylphosphine /methanol solvate, [(PPh₃)₃CuF].- 4PPh₃.4MeOH, is reported together with characterization by solid-state ³¹P CP-MAS n.m.r. and single-crystal X-ray diffraction. Crystals are trigonal, space group P3, with a 14.453(5), c 15.388(6)Ǻ. The structure refined to a final R value of 0.049 for 1926 'observed' [I> 3σ(I)] reflections. The (PPh₃)₃CuF molecule lies on a crystallographic threefold axis. Cu-F is 2.115(9)Ǻ, and Cu-P 2.323(3)Ǻ. The solid-state ³¹P n.m.r. spectrum is dominated by peaks from each of the four solvated PPh₃ molecules at -1.6, -5.4, -10.6 and -14.2 ppm with respect to 85% H₃PO₄. The quartet of lines arising from the ligands coordinated to the copper atom shows an average chemical shift of -5 ppm and approximately equal line spacings of 1.0 kHz.