硼的1,3,2-二氮杂环硼烷衍生的卡宾配合物。

1,3,2-Diazaborole-derived carbene complexes of boron.

作者信息

Hickox Hunter P, Wang Yuzhong, Luedecke Kaitlin M, Xie Yaoming, Wei Pingrong, Carrillo Deidrah, Dominique Nathaniel L, Cui Dongtao, Schaefer Henry F, Robinson Gregory H

机构信息

Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, USA.

出版信息

Dalton Trans. 2017 Dec 19;47(1):41-44. doi: 10.1039/c7dt04079b.

DOI:10.1039/c7dt04079b

PMID:29168513

Abstract

Reaction of 2-bromo-1,3,2-diazaborole (1) with excess BBr induces 1,2-hydrogen migration, giving 1,3,2-diazaborole-derived carbene complexes of boron bromide (2). Compound 2 exists in a dynamic solution equilibrium with 1. The H NMR study shows that the equilibrium lies to the right side of the dissociation reaction of 2. Parallel reaction of 1 with excess BI gives the corresponding 1,3,2-diazaborole-derived carbene boron iodide complex (3). Notably, in contrast to 2, the dissociation reaction of 3 largely lies to the left side, favouring the formation of 3. The dynamic solution equilibrium behaviours of 2 and 3 are probed by both experimental and theoretical methods.

摘要

2-溴-1,3,2-二氮杂硼环戊烷（1）与过量的BBr反应会引发1,2-氢迁移，生成源自1,3,2-二氮杂硼环戊烷的溴化硼卡宾配合物（2）。化合物2与1存在动态溶液平衡。1H NMR研究表明，该平衡位于2的解离反应的右侧。1与过量BI的平行反应生成相应的源自1,3,2-二氮杂硼环戊烷的碘化硼卡宾配合物（3）。值得注意的是，与2相反，3的解离反应很大程度上位于左侧，有利于3的形成。通过实验和理论方法对2和3的动态溶液平衡行为进行了探究。