Smith Jesse E, Gabbaï François P
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Organometallics. 2023 Jan 30;42(3):240-245. doi: 10.1021/acs.organomet.2c00565. eCollection 2023 Feb 13.
As part of our investigations into the Lewis acidic behavior of antimony derivatives, we have decided to study the properties of 5-phenyl-5,5-dichloro-λ-dibenzostibole (), a dichlorostiborane with an antimony atom confined to a five-membered heterocycle. Our work shows that the resulting geometrical constraints elevate the Lewis acidity of the antimony atom, as confirmed by the crystal structure of -THF and the solution study of the interaction of with PhPO. The enhanced Lewis acidic properties of , which exceed those of simple dichlorostiboranes such as PhSbCl, also become manifest in pnictogen bonding catalysis experiments involving the reductions of imines with Hantzsch ester. The influence of geometrical constraints in the chemistry of this compound is also supported by a computational activation strain analysis as well as by an energy decomposition analysis of a model MePO adduct.
作为我们对锑衍生物路易斯酸性行为研究的一部分，我们决定研究5-苯基-5,5-二氯-λ-二苯并锑硼烷（）的性质，这是一种二氯锑硼烷，其中锑原子被限制在一个五元杂环中。我们的研究表明，由此产生的几何限制提高了锑原子的路易斯酸性，这一点通过-THF的晶体结构以及与PhPO相互作用的溶液研究得到了证实。的增强路易斯酸性性质超过了简单的二氯锑硼烷如PhSbCl，这在涉及用汉斯酯还原亚胺的氮族元素键催化实验中也很明显。该化合物化学中几何限制的影响也得到了计算活化应变分析以及模型MePO加合物的能量分解分析的支持。
