Ganesamoorthy C, Matthias M, Bläser D, Wölper C, Schulz S
Institute of Inorganic Chemistry, University of Duisburg-Essen, 45117 Essen, Germany.
Dalton Trans. 2016 Jul 28;45(28):11437-44. doi: 10.1039/c6dt01688j. Epub 2016 Jun 24.
Lewis acid-base adducts [LGa-M(C6F5)3] (M = B 1, Al 2, Ga 3) were prepared by the reaction of gallanediyl LGa {L = HC[C(Me)N(2,6-i-Pr2C6H3)]2} with the Lewis acids M(C6F5)3 (M = B, Al, Ga). Benzaldehyde reacts with [LGa-M(C6F5)3] (M = B 1, Al 2) at room temperature with the insertion and formation of [LGa(C6F5){CH(Ph)(OB(C6F5)2)}] (4) and the zwitterionic species [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] (5), respectively, which was found to decompose at 80 °C with the formation of {(C6F5)2Al(OCH2Ph)}2 (6). Any attempts to isolate the insertion complex of [LGa-Ga(C6F5)3] with benzaldehyde failed and only {(C6F5)2Ga(OCH2Ph)}2 (7) was isolated at elevated temperatures. 2-5 and 7 were structurally characterized by heteronuclear NMR spectroscopy and single crystal X-ray diffraction.
通过镓二价体LGa {L = HC[C(Me)N(2,6-i-Pr2C6H3)]2} 与路易斯酸M(C6F5)3 (M = B、Al、Ga) 反应制备了路易斯酸碱加合物[LGa-M(C6F5)3] (M = B 1、Al 2、Ga 3)。室温下，苯甲醛与[LGa-M(C6F5)3] (M = B 1、Al 2) 反应，分别插入并形成[LGa(C6F5){CH(Ph)(OB(C6F5)2)}] (4) 和两性离子物种[LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] (5)，发现其在80 °C分解形成{(C6F5)2Al(OCH2Ph)}2 (6)。分离[LGa-Ga(C6F5)3] 与苯甲醛插入配合物的所有尝试均失败，仅在高温下分离得到{(C6F5)2Ga(OCH2Ph)}2 (7)。通过异核核磁共振光谱和单晶X射线衍射对2 - 5和7进行了结构表征。
