STRUCTURAL AND SPECTROSCOPIC COMPARISONS OF TRIS(2-(DIPHENYLPHOSPHINO)ETHYL)AMINECOPPER(I) TETRAPHENYLBORATE, [(NP3)CU](BPH4), WITH GOLD(I)) AND SILVER(I) [(NP3)M]X (X = BPH4, NO3, PF6) COMPLEXES

The ligand tris(2-(diphenylphosphino)ethyl)amine (NP3) reacts with CuC l in CH2Cl2 to produce the monomeric complex [(NP3)Cu](BPh4), (1). Unl ike the Au(I) and Ag(I) derivatives, this material is weakly 4-coordin ate with a trigonal CuP3 coordination and somewhat long Cu-N bonding t o the tertiary N atom. Compound 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with cell constants: a = 21.068(8) Angstrom, b = 18.546(2) Angstrom, c = 31.523(6) Angstrom, beta = 107.02(2)degrees and Z = 8. Refinement of 12572 reflections and 1075 parameters yields R = 0.0927 and Rw = 0.1980. This structure completes the Cu, Ag, Au t riad of NP3 complexes. The 3-coordinate mononuclear and binuclear Au(I ) NP3 complexes, [(NP3)Au]X (X = BPh4, PF6, NO3) and [(NP3)(2)Au-2]X-2 (X = BPh4, PF6), all show a brilliant luminescence under UV radiation . This emission has been studied in detail and is attributed to a meta l-centered p(z) --> (d(x2-y2), d(xy)) transition. The Cu(I) complex is not luminescent in the visible spectral region. (C) 1998 Elsevier Sci ence B.V. All rights reserved.