Lehrstuhl für Anorganische Chemie und Strukturchemie and Centrum für molekulare Materialien CM2, Fakultät für Chemie, Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld (Germany).
Angew Chem Int Ed Engl. 2015 Nov 2;54(45):13416-9. doi: 10.1002/anie.201504171. Epub 2015 Oct 1.
Frustrated Lewis pairs (FLPs) have a great potential for activation of small molecules. Most known FLP systems are based on boron or aluminum atoms as acid functions, few on zinc, and only two on boron-isoelectronic silicenium cation systems. The first FLP system based on a neutral silane, (C2F5)3SiCH2P(tBu)2 (1), was prepared from (C2F5)3SiCl with C2F5 groups of very high electronegativity and LiCH2P(tBu)2. 1 is capable of cleaving hydrogen, and adds CO2 and SO2. Hydrogen splitting was confirmed by H/D scrambling reactions. The structures of 1, its CO2 and SO2 adducts, and a decomposition product with CO2 were elucidated by X-ray diffraction.
受阻路易斯对(FLPs)在小分子的活化方面具有巨大的潜力。大多数已知的 FLP 体系都是基于硼或铝原子作为酸官能团,少数是锌,只有两个是基于硼等电子硅阳离子体系。第一个基于中性硅烷的 FLP 体系,(C2F5)3SiCH2P(tBu)2 (1),是由具有非常高电负性的 C2F5 基团的 (C2F5)3SiCl 和 LiCH2P(tBu)2 制备得到的。1 能够裂解氢,并与 CO2 和 SO2 加成。通过 H/D scrambling 反应证实了氢的分裂。通过 X 射线衍射解析了 1 的结构、其 CO2 和 SO2 加合物以及具有 CO2 的分解产物的结构。