Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse,CNRS, 118 route de Narbonne, F-31062, Toulouse, France.
Institut de Chimie de Toulouse (FR 2599) UPS, and CNRS, ICT UAR2599, 118 route de Narbonne, F-31062, Toulouse, France.
Chemistry. 2022 Dec 15;28(70):e202202037. doi: 10.1002/chem.202202037. Epub 2022 Oct 26.
Several base-stabilized silyliumylidene ions (2 and 3) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one (2-H and 3 a) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO and H . Moreover, HBPin adduct of 3 a (8-C) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H molecules.
几种不同配体的稳定硅亚基离子（2 和 3）被合成出来。它们的行为似乎强烈依赖于配体的性质。事实上，与由强给电子配体（DMAP、NHC）稳定的反应性差的硅亚基离子 3c、d 相反，硅烯和硫醚支撑的硅亚基离子（2-H 和 3a）对各种小分子表现出更高的反应性。此外，它们通过与硅烷/甲酰胺、CO 和 H2 的连续反应过程，明显展示了它们连续激活多种小分子的能力。此外，3a 的 HBPin 加合物（8-C）催化吡啶的硼氢化反应。特别有趣的是，硅烯支撑的硅亚基硅亚基离子 2-H 是能够激活两个 H 分子的少数物种之一。
