title: Group 10 and 11 metal boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au+) derived from a triphosphine-borane.
abstract: 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] 2-8 (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 sigma-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.
authors: Laboratoire Hétérochimie Fondamentale et Appliquée (UMR-CNRS 5069) and Structure Fédérative Toulousaine en Chimie Moléculaire (FR 2599), Université Paul Sabatier, 118, route de Narbonne, F-31062 Toulouse Cedex 09, France.
authors: Marie
authors: M
authors: Sircoglou
authors: Sébastien
authors: S
authors: Bontemps
authors: Ghenwa
authors: G
authors: Bouhadir
authors: Nathalie
authors: N
authors: Saffon
authors: Karinne
authors: K
authors: Miqueu
authors: Weixing
authors: W
authors: Gu
authors: Maxime
authors: M
authors: Mercy
authors: Chun-Hsing
authors: CH
authors: Chen
authors: Bruce M
authors: BM
authors: Foxman
authors: Laurent
authors: L
authors: Maron
authors: Oleg V
authors: OV
authors: Ozerov
authors: Didier
authors: D
authors: Bourissou
mesh_terms: D001880:Boranes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D006046:Gold / Q000737:chemistry; D017612:Gold Compounds / Q000737:chemistry; D007854:Lead / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory; D018030:Silver Compounds / Q000737:chemistry
chemical_list: D001880:Boranes; D017612:Gold Compounds; D008670:Metals; D009942:Organometallic Compounds; D010720:Phosphines; D018030:Silver Compounds; C038016:gold chloride; D007854:Lead; D010165:Palladium; D006046:Gold; D003300:Copper; D009532:Nickel; C028419:cuprous chloride; C037548:silver chloride