School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P. R. China.
Institute of Inorganic Chemistry, Georg-August-Universität Göttingen, Tammannstrasse 4, 37077, Göttingen, Germany.
Chemistry. 2019 Sep 12;25(51):11918-11923. doi: 10.1002/chem.201902000. Epub 2019 Aug 13.
The effective catalytic activity of organoaluminum compounds for the monohydroboration of carbodiimides has been demonstrated. Two aluminum complexes, 2 and 3, were synthesized and characterized. The efficient catalytic performances of four aluminum hydride complexes L AlH (L =HC(CMeNAr) , Ar=2,6-Et C H ; 1), L AlH (NMe ) (L =o-C H F(CH=N-Ar), Ar=2,6-Et C H ; 2), L AlH (L =2,6-bis(1-methylethyl)-N-(2-pyridinylmethylene)phenylamine; 3), and L AlH(NMe ) (L =o-C H (N-Dipp)(CH=N-Dipp), Dipp=2,6-iPr C H ; 4), and an aluminum alkyl complex L AlMe (5) were used for the monohydroboration of carbodiimides investigated under solvent-free and mild conditions. Compounds 1-3 and 5 can produce monohydroborated N-borylformamidine, whereas 4 can afford the C-borylformamidine product. A suggested mechanism of this reaction was explored, and the aluminum formamidinate compound 6 was characterized by single-crystal X-ray, also a stoichiometric reaction was investigated.
有机铝化合物对碳二亚胺的单氢硼化具有有效的催化活性。合成并表征了两种铝配合物 2 和 3。四种铝氢化物配合物 L AlH（L=HC（CMeNAr），Ar=2,6-Et C H；1）、L AlH（NMe ）（L=o-C H F（CH=N-Ar），Ar=2,6-Et C H；2）、L AlH（L=2,6-双（1-甲基乙基）-N-（2-吡啶基亚甲基）苯基胺；3）和 L AlH（NMe ）（L=o-C H（N-Dipp）（CH=N-Dipp），Dipp=2,6-iPr C H；4）以及铝烷基配合物 L AlMe（5）在无溶剂和温和条件下被用于碳二亚胺的单氢硼化反应。化合物 1-3 和 5 可以生成单氢硼化的 N-硼基甲脒，而 4 可以得到 C-硼基甲脒产物。探索了该反应的可能机理，并通过单晶 X 射线对铝甲脒化合物 6 进行了表征，还研究了其计量反应。
