Organoaluminum Silylamido Complexes

The reaction between [Et2AlCl] and 1 equiv of HN(SiMe3)2 in CH2Cl2 afforded colorless
crystals of [Et2AlCl{NH(SiMe3)2}] (1). In contrast, reaction of [Et2AlCl] with 1 equiv of HN(SiMe2H)2 or HNtBu(SiMe3) resulted in the isolation of dimers, of the type [EtAlCl{NH(R‘)}]2 (2, R‘ = SiMe2H; 3, R‘ = tBu). Reaction of [Et3Al] with 1 equiv of HN(SiMe2H)2 or
HN(SiMe3)2 yielded the expected dimeric complexes, [Et2Al{N(SiMe2H)2}]2 (4) and [Et2Al{N(SiMe3)2}]2 (5), via ethane elimination. The related reaction between [MeAlCl2] and HNtBu(SiMe3) in CH2Cl2 solution resulted in the formation of the 1:1 adduct [MeAlCl2{NH2(tBu)}]
(6). The structures of compounds 1 and 6 have been determined by X-ray crystallography.
In addition, the decomposition of 1 and 6 has been studied by thermal gravimetric analysis.

将二乙基氯化铝([Et₂AlCl])与1当量的六甲基二硅氮烷(HN(SiMe₃)₂)在二氯甲烷(CH₂Cl₂)中反应，得到无色晶体产物[Et₂AlCl{NH(SiMe₃)₂}]（标记为1）。与之不同，[Et₂AlCl]分别与1当量的HN(SiMe₂H)₂或N-叔丁基三甲基硅基胺(HNtBu(SiMe₃))反应时，可分离得到通式为[EtAlCl{NH(R′)}]₂的二聚体（2：R′=SiMe₂H；3：R′=叔丁基(tBu)）。三乙基铝([Et₃Al])与1当量的HN(SiMe₂H)₂或六甲基二硅氮烷发生乙烷消除反应，生成预期的二聚体配合物[Et₂Al{N(SiMe₂H)₂}]₂（4）与[Et₂Al{N(SiMe₃)₂}]₂（5）。另一相关反应中，二氯甲基铝([MeAlCl₂])与N-叔丁基三甲基硅基胺在二氯甲烷溶液中反应，得到1:1加合物[MeAlCl₂{NH₂(tBu)}]（6）。配合物1与6的结构已通过X射线晶体衍射(X-ray crystallography)确定。此外，研究人员还通过热重分析(thermal gravimetric analysis)对配合物1和6的热分解过程进行了研究。