Bis(functionalized NHC) Palladium(II) Complexes via a Postmodification Approach

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• 作者：Qiaoqiao Teng ; Daniel Upmann ; Sheena Ai Zi Ng Wijaya ; Han Vinh Huynh
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 14, 2014
• 年：2014
• 卷：33
• 期：13
• 页码：3373-3384
• 全文大小：541K
• ISSN：1520-6041

文摘

A series of 20 bis(functionalized NHC) Pd(II) complexes have been conveniently synthesized through postmodification reactions of the common parent NHC complexes trans-[PdBr₂(C₃Br-bimy)₂] (1a) and trans-[PdBr₂(C₃Br-imy)₂] (1b) (C₃Br-bimy = 1-benzyl-3-(3-bromopropyl)benzimidazolin-2-ylidene and C₃Br-imy = 1-benzyl-3-(3-bromopropyl)imidazolin-2-ylidene) with an N-C₃Br tether. Depending on the nature of the nucleophiles added, competing bromido ligand displacements also occurred. In comparison to the conventional access to functionalized NHC complexes, which involves metalation of individually prefunctionalized azolium salts, this highly modular method proves more effective in cost and time savings. The tetraalkylammonium-functionalized complex trans-[PdBr₂(C₃NEt₃-bimy)₂]Br₂ (14) as a product of the second-generation postmodification of complex 1a was also tested for its catalytic activity in Mizoroki鈥揌eck coupling reactions to study and model the effect of a catalytic amount of ammonium salt additive in Pd-catalyzed C鈥揅 coupling reactions. The ammonium functionalities in this complex exhibit a positive effect on the catalysis in comparison to its parent complexes.