Sircoglou Marie, Bontemps Sébastien, Bouhadir Ghenwa, Saffon Nathalie, Miqueu Karinne, Gu Weixing, Mercy Maxime, Chen Chun-Hsing, Foxman Bruce M, Maron Laurent, Ozerov Oleg V, Bourissou Didier
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.
J Am Chem Soc. 2008 Dec 10;130(49):16729-38. doi: 10.1021/ja8070072.
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.
双亲性三膦硼烷配体1{TPB = [o-iPr2P-(C6H4)3B}能轻易地与所有第10族和第11族金属配位，得到一系列完整的金属硼杂环丁烷(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+)。光谱和结构表征明确证实了所有这些配合物中都存在M - B相互作用。首次提供了硼烷与铜和银配位的证据，并且表明在脱去氯后Au→B相互作用依然存在。实验和理论分析表明，M→B相互作用在Pt和Au配合物中最强。证实了金属氧化态和电荷的影响，并讨论了相对论效应的后果。发现σ受体硼烷配体的配位会导致紫外可见光谱发生显著的红移，Ni、Pd和Pt配合物在可见光范围内有强烈吸收。此外，所有第10族和第11族金属硼杂环丁烷在固态和溶液中均采用C3对称性。发现中心M→B相互作用对这些三叶螺旋桨的螺旋度和构型稳定性有适度影响，密度泛函理论计算支持了反转过程的解离途径。
