作者:Ibrahim Abdellah、Christine Lepetit、Yves Canac、Carine Duhayon、Remi Chauvin
DOI:10.1002/chem.201001721
日期:2010.11.22
trapped in situ by protonation to the corresponding phosphine–benzimidazolium cation. When the chloride anion reacts with the cationic [Pd(η2‐BIMIONAP)Cl2] complex, the same cleavage occurs and the phosphine–NHC moiety is trapped in the corresponding [PdCl2(η2‐phosphine–NHC)] complex. When the chloride anion reacts with the dicationic [Pd(π‐allyl)(η2‐BIMIONAP)]+ complex, allyldiphenylphosphine is produced
尽管先前已通过与过渡金属中心的络合说明了α-ami基膦的外部亲核反应性,但本文使用BIMIONAP研究了其内部亲电反应性(BIMIONAP = N-甲基化的BIMINAP阳离子,BIMINAP =缩写词BIMIP =的形式收缩) 2,2'-双(二苯基膦基)-1,1'-联苯并咪唑和BINAP = 2,2'-双(二苯基膦基)-1,1'-联萘基)。的四乙基氯化铵与自由BIMIONAP反应被发现诱导的N异裂2 ç P键,得到氯二苯膦和通过质子化困在原位成相应的膦-苯并咪唑瞬态膦- N-杂环卡宾(NHC)物种阳离子。当氯阴离子与阳离子[Pd(η2 -BIMIONAP)氯2 ]络合物,发生相同的裂解和膦- NHC部分被捕获在相应的[的PdCl 2(η 2 -膦-NHC)]络合物。当与氯阴离子反应的双阳离子[钯(π烯丙基)(η 2 -BIMIONAP)] +络合物,allyldiphenylphosphine产生,并且[的PdCl(η