Studies of a Novel Catalytic System of B(C6F5)3 and Ammonium Hydrochlorides

doi:10.6023/A15050371

Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (10): 1025-1030.DOI: 10.6023/A15050371 Previous Articles Next Articles

Article

新型B(C₆F₅)₃/有机胺盐酸盐催化体系的反应研究

胡茜, 田冲, Borzov Maxim, 聂万丽

天然产物与小分子合成四川省高校重点实验室乐山师范学院化学学院乐山 614000

投稿日期:2015-06-05 发布日期:2015-07-17
通讯作者: 聂万丽 E-mail:niewl126@126.com
基金资助:
国家自然科学基金资助项目(Nos.21072157,20702041)和乐山师范学院校级重点实验室资助项目(Z1308).

Studies of a Novel Catalytic System of B(C₆F₅)₃ and Ammonium Hydrochlorides

Hu Xi, Tian Chong, Borzov Maxim, Nie Wanli

Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department, Leshan Normal University, Leshan 614000, China

Received:2015-06-05 Published:2015-07-17
Supported by:
Project supported by the National Science Foundation of China (Nos. 21072157, 20702041), and the Key Laboratory Foundation of Leshan Normal University (Z1308).

1. Studies of a Novel Catalytic System of B(C₆F₅)₃ and Ammonium Hydrochlorides.PDF(210KB)

Abstract

In modern practice, frustrated Lewis pairs (FLPs) are well-known to exhibit unique chemical properties in respect to H₂ activation. Additionally, CO₂ catalytic reduction and related catalytic hydrogenations of unsaturated bonds have also been widely concerned. This paper describes designation and studies of a novel FLP catalyst system, in which the Lewis base component is introduced as an amine hydrochloride (not a free amine), while the Lewis acid component is retained [tris(pentafluorophenyl)borane, B(C₆F₅)₃ (BCF)]. With a hydridosilane as a source of the hydride, this novel system, at first, presents a new facile synthetic approach to ammonium hydridoborates [R₃NH]⁺[HBCF]^-. Remarkably, that irrespective of the bulkiness of the ammonium component, various primary, secondary and tertiary ammonium salts with HBCF^- anion can all be prepared by the suggested procedure under mild conditions and in high yields. At the same time this system may serve as a powerful tool for selective and exhaustive reduction of organic carbonyl compounds and even CO₂ down to alkanes and methane, respectively. Comparison of the ¹H NMR spectra of the starting hydrochlorides, the intermediate ammonium chloroborates [R₃NH]⁺[ClBCF]^-, and [R₃NH]⁺[HBCF]^- reveals that the appearance of the NH signals is strongly dependent upon the nature of the counterion. While in the parent chlorides signals of these protons are observed as broad singlets or multiplets due to the quadrupolar relaxation on the adjacent ¹⁴N nucleus, in the spectra of their [HBCF]^- analogues these signals exhibit distinct fine structure due to the spin-spin coupling with the ¹⁴N [¹J(¹⁴N-H)≈50 Hz; 1︰1︰1 triplets]. The latter is indicative of the increase of the symmetry of the electric field at the ¹⁴N nucleus location along with the decrease of the degree of ammonium/anoin interaction. The chemical reactivity of these [HBCF]^- analogues is interesting matched with their NH signals．

Key words: frustrated Lewis pairs, tris(pentafluorophenyl)boron, ammonium chlorides, silanes, ammonium hydridoborates

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Hu Xi, Tian Chong, Borzov Maxim, Nie Wanli. Studies of a Novel Catalytic System of B(C₆F₅)₃ and Ammonium Hydrochlorides[J]. Acta Chim. Sinica, 2015, 73(10): 1025-1030.

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新型B(C₆F₅)₃/有机胺盐酸盐催化体系的反应研究

Studies of a Novel Catalytic System of B(C₆F₅)₃ and Ammonium Hydrochlorides

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新型B(C6F5)3/有机胺盐酸盐催化体系的反应研究