化学学报
化學學報
화학학보
ACTA CHIMICA SINICA
2007年
20期
2320-2324
,共5页
尹传奇%陈瑶%冯权武%柏正武%王长芳%李早英
尹傳奇%陳瑤%馮權武%柏正武%王長芳%李早英
윤전기%진요%풍권무%백정무%왕장방%리조영
单氢钌配合物%原位核磁共振%分子间氢键%反应中间体%反应机理
單氫釕配閤物%原位覈磁共振%分子間氫鍵%反應中間體%反應機理
단경조배합물%원위핵자공진%분자간경건%반응중간체%반응궤리
利用原位1H和31p NMR对单氢钌配合物TpRu(PPh3)(CH3CN)H[Tp=hydrotris(pyrazolyl)borate]与H2O和酸性HOCH2CF3的反应进行了研究,结果显示相应的反应产物分别是TpRu(PPh3)(CH3CN)(OH)和TpRu(PPh3)(CH3CN)(OCH2CF3).观察到反应过程中Ru-H…HOH和Ru-H…HOCH2CF3分子间的氢键作用.提出了生成TpRu(PPh3)(CH3CN)(OH)和TpRu(PPh3)(CH3CN)(OCH2CF3)的不同作用机理.在水存在下,TpRu(PPh3)(CH3CN)H与H2O反应,经过中间体TpRu(PPh3)(H2O)H和TpRu(PPh3)(OH)(η2-H2)生成产物TpRu(PPh3)(CH3CN)(OH).而TpRu(PPh3)(CH3CN)H与酸性HOCH2CF3反应时,单氢配体被质子化形成中间体[TpRu(PPh3)(CH3CN)-(η2-H2)](OCH2CF3),进而转变成产物TpRu(PPh3)(CH3CN)(OCH2CF3).TpRu(PPh3)(CH3CN)(OCH2CF3)与H2作用,经中间体TpRu(PPh3)(HOCH2CF3)H生成TpRu(PPh3)(η2-H2)H.
利用原位1H和31p NMR對單氫釕配閤物TpRu(PPh3)(CH3CN)H[Tp=hydrotris(pyrazolyl)borate]與H2O和痠性HOCH2CF3的反應進行瞭研究,結果顯示相應的反應產物分彆是TpRu(PPh3)(CH3CN)(OH)和TpRu(PPh3)(CH3CN)(OCH2CF3).觀察到反應過程中Ru-H…HOH和Ru-H…HOCH2CF3分子間的氫鍵作用.提齣瞭生成TpRu(PPh3)(CH3CN)(OH)和TpRu(PPh3)(CH3CN)(OCH2CF3)的不同作用機理.在水存在下,TpRu(PPh3)(CH3CN)H與H2O反應,經過中間體TpRu(PPh3)(H2O)H和TpRu(PPh3)(OH)(η2-H2)生成產物TpRu(PPh3)(CH3CN)(OH).而TpRu(PPh3)(CH3CN)H與痠性HOCH2CF3反應時,單氫配體被質子化形成中間體[TpRu(PPh3)(CH3CN)-(η2-H2)](OCH2CF3),進而轉變成產物TpRu(PPh3)(CH3CN)(OCH2CF3).TpRu(PPh3)(CH3CN)(OCH2CF3)與H2作用,經中間體TpRu(PPh3)(HOCH2CF3)H生成TpRu(PPh3)(η2-H2)H.
이용원위1H화31p NMR대단경조배합물TpRu(PPh3)(CH3CN)H[Tp=hydrotris(pyrazolyl)borate]여H2O화산성HOCH2CF3적반응진행료연구,결과현시상응적반응산물분별시TpRu(PPh3)(CH3CN)(OH)화TpRu(PPh3)(CH3CN)(OCH2CF3).관찰도반응과정중Ru-H…HOH화Ru-H…HOCH2CF3분자간적경건작용.제출료생성TpRu(PPh3)(CH3CN)(OH)화TpRu(PPh3)(CH3CN)(OCH2CF3)적불동작용궤리.재수존재하,TpRu(PPh3)(CH3CN)H여H2O반응,경과중간체TpRu(PPh3)(H2O)H화TpRu(PPh3)(OH)(η2-H2)생성산물TpRu(PPh3)(CH3CN)(OH).이TpRu(PPh3)(CH3CN)H여산성HOCH2CF3반응시,단경배체피질자화형성중간체[TpRu(PPh3)(CH3CN)-(η2-H2)](OCH2CF3),진이전변성산물TpRu(PPh3)(CH3CN)(OCH2CF3).TpRu(PPh3)(CH3CN)(OCH2CF3)여H2작용,경중간체TpRu(PPh3)(HOCH2CF3)H생성TpRu(PPh3)(η2-H2)H.
