Electronic and Structural Effects of Stepwise Borylation and Quaternization on Borirene Aromaticity

被引：42

作者：

Braunschweig, Holger ^{[1
]}

Damme, Alexander ^{[1
]}

Dewhurst, Rian D. ^{[1
]}

Ghosh, Sundargopal ^{[2
]}

Kramer, Thomas ^{[1
]}

Pfaffinger, Bernd ^{[1
]}

Radacki, Krzysztof ^{[1
]}

Vargas, Alfredo ^{[1
]}

机构：

[1] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany

[2] Indian Inst Technol, Dept Chem, Madras 600036, Tamil Nadu, India

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 05期

基金：

欧洲研究理事会;

关键词：

BORYLENE TRANSFER; PHOTOPHYSICAL PROPERTIES; ORGANOBORON COMPOUNDS; OPTICAL-PROPERTIES; BORON; COMPLEXES; BOND; COORDINATION; SYSTEMS; REACTIVITY;

D O I：

10.1021/ja3110126

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Room-temperature photolysis of the amino-boryl complex [(OC)(5)Cr=B=N(SiMe3)(2)] in the presence of a series of mono- or bis(boryl) alkynes bis{bis-(dimethylamino)boryl}ethyne, 1-phenyl-2-bis-(dimethylamino)borylethyne, and 1-trimethylsilyl-2-bis-(dimethylamino)borylethyne led to the isolation of hitherto unknown borylborirenes in resonable yields, that is, [(RC=CR')(mu-BN(SiMe3)(2))] (7, R = B(NMe2)(2), R' = Ph; 8, R = R' = B(NMe2)(2); 9, R = B(NMe2)(2), R' = SiMe3). The borirenes were isolated and spectroscopically characterized by multinuclear NMR, IR, and UV/vis spectroscopy, crystallography, and elemental analysis. Reactivity studies of the borirenes demonstrated their behavior toward different Lewis bases. The isolated adducts and the parent borirenes were compared to 1,3-mesityl-2-phenylborirene and its adducts. To gain insight into the electronic structure and to evaluate the influence of the exocyclic groups, Density Functional Theory (DFT) calculations were carried out.

引用

页码：1903 / 1911

页数：9

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