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).

金属取代的硅烯引起了人们的高度关注，因为理论研究表明，带有正电取代基的硅烯具有较小的 Δ E _S−T（单线态-三线态能隙），甚至具有基态三线态。然而，此类化合物非常不稳定，并且仅通过碱金属取代的硅杂环丙烯的光挤出生成了两种瞬态碱金属取代的硅烯M( ^t Bu ₃ Si)Si:(M = Li, K)，并且仅通过光谱方法进行了研究（EPR）在低温（14 至 50 K）下。在此，我们报道了在非常温和和方便的条件下从硅杂环丙基锌配合物生成瞬时锌取代的硅烯。生成的瞬时锌取代的硅烯具有高反应性，并与烯烃进行分子间环加成，合成锌取代的硅杂环化合物。如果没有底物，锌取代的硅烯会攻击 β-二酮亚胺配体的 C-C 键并断裂 C-C 键。DFT 研究进一步强调了锌取代硅烯的硅烯性质和非常小的 Δ E _S−T (4.4 kcal/mol)。