Electronic and Structural Effects of Stepwise Borylation and Quaternization on Borirene Aromaticity
详细信息 查看全文
- 作者：Holger Braunschweig ; Alexander Damme ; Rian D. Dewhurst ; Sundargopal Ghosh ; Thomas Kramer ; Bernd Pfaffinger ; Krzysztof Radacki ; Alfredo Vargas
- 刊名：The Journal of the American Chemical Society
- 出版年：2013
- 出版时间：February 6, 2013
- 年：2013
- 卷：135
- 期：5
- 页码：1903-1911
- 全文大小：510K
- 年卷期：v.135,no.5(February 6, 2013)
- ISSN：1520-5126
文摘
Room-temperature photolysis of the aminoboryl complex [(OC)5Cr鈺怋鈺怤(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鈺怌R鈥?(渭-BN(SiMe3)2)] (7, R = B(NMe2)2, R鈥?= Ph; 8, R = R鈥?= B(NMe2)2; 9, R = B(NMe2)2, R鈥?= 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.