Department of Chemistry, Brock University , 1812 Sir Isaac Brock Way, St. Catharines, Ontario Canada L2S 3A1.
Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona , Carrer Maria Aurèlia Capmany 69, 17003 Girona, Spain.
J Am Chem Soc. 2017 Jul 5;139(26):8804-8807. doi: 10.1021/jacs.7b04841. Epub 2017 Jun 21.
Reaction of the cyclic guanidine TolN═SIMe with the aluminum(I) compound NacNacAl (1) results in the unprecedented cleavage of the C-N multiple bond to give, after rearrangement, the carbene-ligated Al(III) amide, NacNac'Al(NHTol)(SIMe) (6). DFT calculations revealed that these reactions proceed via a bimolecular mechanism in which either the basic Al(I) center or the transient Al═NTol species deprotonates the methyl group of the NacNac ligand.
环状胍 TolN═SIMe 与铝（I）化合物 NacNacAl（1）反应，导致 C-N 多重键的空前断裂，经过重排后，得到卡宾配位的 Al(III)酰胺 NacNac'Al(NHTol)(SIMe)（6）。DFT 计算表明，这些反应通过双分子机制进行，其中要么是碱性 Al(I)中心，要么是瞬态 Al═NTol 物种，使 NacNac 配体的甲基去质子化。
