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Where silylene-silicon centres matter in the activation of small molecules.
Chemical Society Reviews ( IF 46.2 ) Pub Date : 2020-08-19 , DOI: 10.1039/d0cs00815j
Changkai Shan 1 , Shenglai Yao 1 , Matthias Driess 1
Affiliation  

Small molecules such as H2, N2, CO, NH3, O2 are ubiquitous stable species and their activation and role in the formation of value-added products are of fundamental importance in nature and industry. The last few decades have witnessed significant advances in the chemistry of heavy low-coordinate main-group elements, with a plethora of newly synthesised functional compounds, behaving like transition-metal complexes with respect to facile activation of such small molecules. Among them, silylenes have received particular attention in this vivid area of research showing even metal-free bond activation and catalysis. Recent striking discoveries in the chemistry of silylenes take advantage of narrow HOMO–LUMO energy gap and Lewis acid–base bifunctionality of divalent Si centres. The review is devoted to recent advances of using isolable silylenes and corresponding silylene–metal complexes for the activation of fundamental but inert molecules such as H2, COx, N2O, O2, H2O, NH3, C2H4 and E4 (E = P, As).

中文翻译:

甲硅烷基硅中心与小分子的活化有关。

小分子,例如H 2,N 2,CO,NH 3,O 2是普遍存在的稳定物种,它们的激活和在增值产品的形成中的作用在自然界和工业界都至关重要。在过去的几十年中,重的低配位主族元素的化学反应取得了重大进展,其中包括大量新合成的功能性化合物,就这类小分子的易活化而言,其行为类似于过渡金属配合物。其中,在这一生动的研究领域中,即使无金属键的活化和催化作用,甲硅烷基也受到了特别的关注。近期在硅化学中的惊人发现利用了狭窄的HOMO-LUMO能隙和二价Si中心的路易斯酸碱双官能度。在图2中,CO x,N 2 O,O 2,H 2 O,NH 3,C 2 H 4和E 4(E = P,As)。
更新日期:2020-09-21
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