在路易斯酸存在下，[BH]阴离子中的亲核取代反应。

Nucleophilic Substitution Reactions in the [BH] Anion in the Presence of Lewis Acids.

作者信息

Shulyak Alexandra T, Bortnikov Evgeniy O, Selivanov Nikita A, Grigoriev Mikhail S, Kubasov Alexey S, Zhdanov Andrey P, Bykov Alexander Y, Zhizhin Konstantin Y, Kuznetsov Nikolai T

机构信息

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia.

Inorganic Chemistry Department, Lomonosov Institute of Fine Chemical Technologies, MIREA-Russian Technological University, Pr. Vernadskogo, 86, 119454 Moscow, Russia.

出版信息

Molecules. 2022 Jan 24;27(3):746. doi: 10.3390/molecules27030746.

DOI:10.3390/molecules27030746

PMID:35164015

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8838051/

Abstract

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, PhP, PhP-(CH)-PPh (dppe), PhAs, EtN, PhNH, CHN, CHCN, PhCHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [BHNu] are obtained. It is found that the use of TiCl, AlCl, ZrCl, HfCl, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [BH-HMXn], which was detected by NMR spectroscopy. The structures of [PhP·BH] and [PhNH·BH] were determined by X-ray diffraction.

摘要

我们研究了在多种路易斯酸（Ti(IV)、Hf(IV)、Zr(IV)、Al、Cu(I)、Zn、Mn(II)、Co(II)卤化物和碘）存在下，八氢三硼酸根阴离子与亲核试剂（Nu = THF、PhP、PhP-(CH)-PPh（dppe）、PhAs、EtN、PhNH、CHN、CHCN、PhCHCN）之间的相互作用，结果得到了多种八氢三硼酸根阴离子的取代衍生物[BHNu]。发现使用TiCl、AlCl、ZrCl、HfCl、CuCl和碘时产物产率最高。在这种情况下，反应很可能通过形成中间体[BH-HMXn]进行，该中间体通过核磁共振光谱检测到。通过X射线衍射确定了[PhP·BH]和[PhNH·BH]的结构。