Carbene-Bound Borane and Silane Adducts: A Comprehensive DFT Study on Their Stability and Propensity for Hydride-Mediated Ring Expansion

被引：71

作者：

Momeni, Mohammad R. ^{[1
]}

Rivard, Eric ^{[1
]}

Brown, Alex ^{[1
]}

机构：

[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 21期

基金：

加拿大自然科学与工程研究理事会;

关键词：

N-HETEROCYCLIC CARBENES; CORRELATED MOLECULAR CALCULATIONS; POLARIZABLE CONTINUUM MODEL; GAUSSIAN-BASIS SETS; ELECTRONIC-STRUCTURE; BOND ACTIVATION; MAIN-GROUP; B-H; CYANOSILYLATION; COMPLEXES;

D O I：

10.1021/om400791r

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The stability of a variety of borane (BH3 and BH2NHMe) and silane (SiHnPh4-n, n = 0-4) adducts with diamino (NHC) and aminoalkyl (CAAC) carbenes has been carefully examined using M06-2X/cc-pVDZ computations, including natural bond orbital and atoms-in-molecules analyses. Moreover a potential mechanism for the hydride-mediated ring expansion of the carbene donors is reported. While the NHC adducts can undergo thermally induced ring-expansion chemistry, the CAAC adducts show increased stability due to a large energetic barrier for the insertion of boron (or silicon) atoms into the CAAC heterocycle. A series of substituted NHCs were investigated to further explore the roles of both electronic and steric effects on adduct stabilities and on their propensities for undergoing ring-expansion transformations.

引用

页码：6201 / 6208

页数：8

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