C–CN Bond Cleavage Using Palladium Supported by a Dippe Ligand

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• 作者：Lloyd Munjanja ; Coralys Torres-López ; William W. Brennessel ; William D. Jones
• 刊名：Organometallics
• 出版年：2016
• 出版时间：June 13, 2016
• 年：2016
• 卷：35
• 期：11
• 页码：2010-2013
• 全文大小：390K
• 年卷期：0
• ISSN：1520-6041

文摘

The (dippe)palladium(0) fragment generated from [(dippe)Pd(μ-H)]₂ (1) has been shown to form an intermediate η²-nitrile complex with acetonitrile (dippe)Pd(η²-C,N-CH₃CN-BEt₃) (2a) in the presence of BEt₃ [(dippe = bis-diisopropylphosphino)ethane)]. On introducing a solution of 2a to 1 equiv of BPh₃, rapid formation of (dippe)Pd(η²-C,N-CH₃CNBPh₃) (2a′) is observed. Heating 2a′ at 100 °C in THF-d₈ results in the C–CN activation product 3a′, (dippe)Pd(CH₃)(CNBPh₃). Reaction of 1 with benzonitrile in the presence of BEt₃ gives the C–CN activation product (dippe)Pd(Ph)(CN-BEt₃) (3b) exclusively. The complexes 2a, 2a′, 3a′, and 3b were characterized by ¹H, ³¹P{¹H}, and ¹³C{¹H} NMR spectroscopy, elemental analysis, IR spectroscopy, and X-ray diffraction.