Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt0 Complexes |
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| Authors: | Nicole Arnold Prof. Dr. Holger Braunschweig Dr. Peter B. Brenner Dr. Mehmet Ali Celik Dr. Rian D. Dewhurst Dr. Martin Haehnel Dr. Thomas Kramer Dr. Ivo Krummenacher Prof. Dr. Todd B. Marder |
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| Affiliation: | Institut für Anorganische Chemie, Julius‐Maximilians‐Universit?t Würzburg, Am Hubland, 97074 Würzburg (Germany) |
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| Abstract: | An improved synthetic route to homoleptic complex [Pt(CAACMe)2] (CAAC=cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAACMe)(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal‐only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero‐valent complexes were explored in concert with density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC‐containing Pt0 complexes was investigated by TD‐DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding π interactions between Pt and the CAAC carbon atoms. |
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| Keywords: | carbenes Lewis bases oxidative addition phosphine ligands platinum |
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