Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties |
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Authors: | Prof. Dr. Holger Braunschweig Christopher K. L. Brown Dr. Rian D. Dewhurst Dr. J. Oscar C. Jimenez‐Halla Thomas Kramer Dr. Ivo Krummenacher Dr. Bernd Pfaffinger |
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Affiliation: | 1. Institut für Anorganische Chemie, Julius‐Maximilians‐Universit?t Würzburg, Am Hubland, 97074 Würzburg (Germany);2. Department of Chemistry (DCNE), Universidad de Guanajuato, Noria Alta s/n 36050 Guanajuato (Mexico) |
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Abstract: | The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes2)(PiPr3)2] and trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes2)(IMe)(PiPr3)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?CBMes2)(IMe)(PiPr3)2]. |
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Keywords: | alkynyl ligands boron rhodium solvatochromism vinylidene ligands |
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