Xu Maotong, Possart Josephine, Waked Alexander E, Roy Julie, Uhl Werner, Stephan Douglas W
Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5H 3H6.
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28-30, 48149 Münster, Germany.
Philos Trans A Math Phys Eng Sci. 2017 Aug 28;375(2101). doi: 10.1098/rsta.2017.0014.
The Lewis acids Ga(CF), In(CF) and Ga(CCl) are prepared and their Lewis acidity has been probed experimentally and computationally. The species Ga(CF) and In(CF) in conjunction with phosphine donors are shown to heterolytically split H and catalyse the hydrogenation of an imine. In addition, frustrated Lewis pairs (FLPs) derived from Ga(CF) and In(CF) and phosphines react with diphenyldisulfide to phosphoniumgallates or indates of the form [BuPSPh][PhSE(CF)] and [BuPSPh][(μ-SPh)(E(CF))] (E = Ga, In). The potential of the FLPs based on Ga(CF), In(CF) and Ga(CCl) and phosphines is also shown in reactions with phenylacetylene to give pure or mixtures of the products [BuPH][PhCCE(CX)] and RP(Ph)C=C(H)E(CX) A number of these species are crystallographically characterized. The implications for the use of these species in FLP chemistry are considered.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.
制备了路易斯酸Ga(CF)、In(CF)和Ga(CCl)，并通过实验和计算对它们的路易斯酸性进行了探究。结果表明，Ga(CF)和In(CF)与膦供体结合能异裂分解H，并催化亚胺的氢化反应。此外，由Ga(CF)、In(CF)和膦衍生的受阻路易斯对（FLPs）与二苯基二硫化物反应，生成形式为[BuPSPh][PhSE(CF)]和[BuPSPh][(μ-SPh)(E(CF))]（E = Ga、In）的鏻鎓镓酸盐或铟酸盐。基于Ga(CF)、In(CF)和Ga(CCl)以及膦的FLPs在与苯乙炔反应生成产物[BuPH][PhCCE(CX)]和RP(Ph)C=C(H)E(CX)的纯品或混合物的反应中也显示出了潜力。其中一些物种通过晶体学进行了表征。本文还考虑了这些物种在FLP化学中的应用意义。本文是主题为“受阻路易斯对化学”的特刊的一部分。
