介绍了几种用 O 2、Et 3 P=O 或 N 2 O 氧化 β-二酮亚胺化 Al I配合物 (BDI)Al 和 (BDI*)Al (BDI=HC[C(Me)N(DIPP) )] 2,DIPP=2,6-二异丙基苯基;BDI*=HC[C( t Bu)N(DIPP)] 2 )。铝氧烷形成的选择性很大程度上取决于β-二酮亚胺配体的性质、实验程序和溶剂。单核铝氧烷 (BDI)Al=O 和 (BDI*)Al=O 是高反应性中间体,它们不能被分离,但要么聚集以产生反应性较低的二聚体,要么通过骨架 Me 基团或i的内部 C-H 活化而分解公关组。醚类溶剂(如 Et2O)与铝氧烷反应生成 (BDI)Al(OEt)OH 和通过 β-H 消除产生乙烯。在 N 2 O 氧化的情况下,观察到随后与第二当量的 N 2 O 反应形成次亚硝酸盐络合物 (BDI)Al(N 2 O 2 ) 和 (BDI*)Al(N 2 O
Synthesis, Structure, and Reactivity of a Monomeric Iminoalane
作者:Jianfeng Li、Xiaofei Li、Wen Huang、Hongfan Hu、Jianying Zhang、Chunming Cui
DOI:10.1002/chem.201203298
日期:2012.11.26
Monomericiminoalane: A donor‐stabilized monomericiminoalane was prepared by the reaction of 1 with an N‐heterocyclic carbene (see scheme). The X‐ray structure exhibits a very short AlN bond of 1.705(4) Å, which suggests multiple‐bond character. Treatment of the iminoalane with phenyl acetylene, aniline, and carbon monoxide resulted in addition reactions to the formal AlN bond, thus indicating that