American Chemical Society
ja8070072_si_003.cif (27.25 kB)

Group 10 and 11 Metal Boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au+) Derived from a Triphosphine−Borane

Download (27.25 kB)
posted on 2008-12-10, 00:00 authored by Marie Sircoglou, Sébastien Bontemps, Ghenwa Bouhadir, Nathalie Saffon, Karinne Miqueu, Weixing Gu, Maxime Mercy, Chun-Hsing Chen, Bruce M. Foxman, Laurent Maron, Oleg V. Ozerov, Didier Bourissou
The ambiphilic triphosphine−borane ligand 1 {TPB = [o-iPr2P-(C6H4)]3B} readily coordinates to all group 10 and 11 metals to afford a complete series of metal boratranes (TPB)[M] 28 (2: M = Ni, 3: M = Pd, 4: M = Pt, 5: M = CuCl, 6: M = AgCl, 7: M = AuCl, 8: M = Au+). Spectroscopic and structural characterization unambiguously establishes the presence of M→B interactions in all of these complexes. The first evidence for borane coordination to copper and silver is provided, and the Au→B interaction is shown to persist upon chloride abstraction. Experimental and theoretical considerations indicate that the M→B interaction is strongest in the Pt and Au complexes. The influence of the oxidation state and charge of the metal is substantiated, and the consequences of relativistic effects are discussed. The coordination of the σ-acceptor borane ligand is found to induce a significant bathochromic shift of the UV−vis spectra, the Ni, Pd, and Pt complex presenting strong absorptions in the visible range. In addition, all of the group 10 and 11 metal boratranes adopt C3 symmetry both in the solid state and in solution. The central M→B interaction is found to moderately influence the degree of helicity and configurational stability of these three-bladed propellers, and DFT calculations support a dissociative pathway for the inversion process.