中文摘要：

近年来,受限路易斯酸碱对（FLPs：Frustrated Lewis Pairs）在小分子的活化以及在催化还原等方面所表现出的独特反应特性,使得有关FLPs化学的研究受到了国内外广泛的关注.设计了一种新型的FLPs催化体系,该体系以三（五氟苯基）硼（BCF）为路易斯酸,以多种不同取代的有机胺盐酸盐替代常规FLPs中的路易斯碱有机胺.发现利用该体系与氢化硅烷反应,不仅可以高产率地制备分离得到相应的伯、仲、叔硼氢化胺盐;而且还可以这一体系作为催化剂,以氢化硅烷作为还原剂,在常温常压下可高选择性地部分或彻底还原大部分含羰基官能团醛酮等有机化合物.由BCF/2,2,6,6-四甲基哌啶（TMP）盐酸盐组成的催化体系在对CO2催化还原为甲烷的反应中,亦较相应的BCF/TMP体系显示更高的活性.还通过核磁共振详细地对比研究了原料有机胺盐酸盐、中间体氯代硼胺盐以及产物氢化硼胺盐中,胺基氮上质子的核磁共振谱信息,发现不仅胺基上取代基的位阻效应会影响到具有电四极矩性的14N磁性核的弛豫效应,而且阴离子基团的配位强弱对胺基氮上质子的化学位移也会产生较大的影响.

英文摘要：

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 [RaNH]＋[C1BCF]-, 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.