Boryl-Functionalized s-Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties

Holger Braunschweig; Christopher K. L. Brown; Rian D. Dewhurst; J. Oscar C. Jimenez-Halla; Thomas Kramer; Ivo Krummenacher; Bernd Pfaffinger

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Boryl-Functionalized s-Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties

机译：硼基官能化的s-炔基和亚乙烯基铑配合物：合成与电子性能

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The synthesis, reactivity, and properties of borylfunctionalized s-alkynyl and vinylidene rhodium complexes such as trans-[RhCl(=C=CHBMes_2)(PiPr_3)_2] and trans-[Rh(C≡ CBMes_2)(IMe)(PiPr_3)_2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido s-alkynyl complexes in solution. The complex trans-[Rh(C-CBMes_2)(IMe)(PiPr_3)_2] (IMe=1,3-dimethylimidazol- 2-ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans-[Rh(C- CBMes_2)(IMe)(PiPr_3)_2].

机译：诸如反-[RhCl（= C = CHBMes_2）（PiPr_3）_2]和反-[Rh（C≡CBMes_2）（IMe）（PiPr_3）_2等硼烷基官能化的s-炔基和亚乙烯基铑配合物的合成，反应性和性质]。发现在溶液中铑亚乙烯基配合物与相应的氢化s-炔基配合物之间存在平衡。发现复合物反式-[Rh（C-CBMes_2）（IMe）（PiPr_3）_2]（IMe = 1,3-二甲基咪唑-2-亚基）表现出溶剂致变色作用，并且可以被准可逆地氧化和电化学还原。进行密度泛函计算，以确定反应机理并有助于合理化反式-[Rh（C-CBMes_2）（IMe）（PiPr_3）_2]的光物理性质。

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《Chemistry: A European journal》 |2014年第5期|共7页
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Holger Braunschweig; Christopher K. L. Brown; Rian D. Dewhurst; J. Oscar C. Jimenez-Halla; Thomas Kramer; Ivo Krummenacher; Bernd Pfaffinger;
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alkynyl ligands; boron; rhodium; solvatochromism; vinylidene ligands;

机译：炔基配体;硼;铑;溶剂变色;亚乙烯基配体;

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1. Boryl-Functionalized s-Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties [J] . Holger Braunschweig, Christopher K. L. Brown, Rian D. Dewhurst, Chemistry: A European journal . 2014,第5期

机译：硼基官能化的s-炔基和亚乙烯基铑配合物：合成与电子性能
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Boryl-Functionalized s-Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties

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