Generation, bonding and reactivity of transient zinc-substituted silylenes

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Science China Chemistry Pub Date : 2024-01-09 DOI:10.1007/s11426-023-1890-9

Cheng Xu, Thayalan Rajeshkumar, Laurent Maron, Xuebing Leng, Yaofeng Chen

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Abstract

The metal-substituted silylenes are of high interest, as the theoretical studies indicated that the silylenes with electropositive substituents have a small ΔE_S−T (singlet-triplet energy gap) or even the ground-state triplets. However, such compounds are highly unstable, and only two transient alkali metal-substituted silylenes M(^tBu₃Si)Si: (M = Li, K) were generated by photoextrusion of the alkali metal-substituted silacyclopropenes and merely studied by spectroscopic method (EPR) at low temperature (14 to 50 K). Herein, we report the generation of transient zinc-substituted silylenes from zinc silacyclopropanyl complexes under very mild and convenient conditions. The generated transient zinc-substituted silylenes are highly reactive and undergo intermolecular cycloaddition with alkenes for the synthesis of zinc-substituted Si-heterocyclic compounds. If there is no substrate, the zinc-substituted silylenes attack the C-C bonds of the β-diketiminato ligands and break the C-C bonds. DFT studies further highlight the silylene nature of the zinc-substituted silylene and a very small ΔE_S−T (4.4 kcal/mol).

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瞬时锌取代硅烷基的生成、键合和反应性

金属取代的亚甲硅烷基引起了人们的极大兴趣，因为理论研究表明，带有电正性取代基的亚甲硅烷基具有较小的 ΔES-T（单线-三线能隙），甚至是基态三线。然而，这类化合物极不稳定，目前只有两种瞬态碱金属取代的硅烷基烯 M(tBu3Si)Si：（M = Li，K）是通过光挤压碱金属取代的硅烷环丙烯生成的，并且只是在低温（14 至 50 K）下通过光谱法（EPR）进行了研究。在此，我们报告了在非常温和和方便的条件下从硅烷环丙烯锌络合物中生成瞬时锌取代硅烷基的情况。生成的瞬时锌取代硅烷基具有高活性，可与烯烃发生分子间环加成反应，合成锌取代的Si-杂环化合物。如果没有底物，锌取代的硅烷基会攻击 β-二酮配体的 C-C 键，并打断 C-C 键。DFT 研究进一步突出了锌取代的亚甲硅烷基的亚甲硅烷基性质以及非常小的ΔES-T（4.4 kcal/mol）。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.