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Latent Ruthenium Complexes Supported by Two N-Heterocyclic Carbene Ligands: Synthesis and Catalytic Activity with Distinctive Activation
European Journal of Organic Chemistry ( IF 2.7 ) Pub Date : 2025-03-23 , DOI: 10.1002/ejoc.202500284
Anna Vaisman Hosein Tafazolian Diana Stoianova Jonathan M. Goldberg Kristina Goulinian Angelino Doppiu Adam M. Johns Norberto Gabriel Lemcoff

Novel bis(N-heterocyclic carbene [NHC]) ruthenium complexes of the form (NHC1)(NHC2)Ru(=CRR')Cl2 (where NHC represents N-heterocyclic carbene ligands and CRR’ denotes Ph-indenylidene or benzylidene moieties) are prepared from second- and third-generation Grubbs catalysts. These complexes exhibit thermal latency in ring-closing metathesis (RCM), cross-metathesis (CM), and several ring-opening metathesis polymerization (ROMP) reactions. Upon UV-C (255 nm) irradiation, two complexes that contained benzylidene ligands prove to be highly effective for the ROMP of cyclooctadiene. The most active species incorporate IPr or SIPr as at least one NHC ligand, highlighting how bulky isopropyl substituents enhance NHC lability. Beyond their utility in UV-C-initiated ROMP, these complexes show promising activity for high-temperature CM and RCM of alkenyl-nitrile substrates.

中文翻译:

由两个 N-杂环卡宾配体支持的潜在钌配合物:具有独特活化的合成和催化活性

由第二代和第三代 Grubbs 催化剂制备了 (NHC1)(NHC2)Ru(=CRR')Cl2 形式的新型双(N-杂环卡宾 [NHC])钌配合物(其中 NHC 代表 N-杂环卡宾配体,CRR' 表示 Ph-亚丁基或亚苄基部分)。这些复合物在闭环复分解 (RCM)、交叉复分解 (CM) 和几种开环复分解聚合 (ROMP) 反应中表现出热潜伏期。在 UV-C (255 nm) 照射下,含有亚苄基配体的两个复合物被证明对环辛二烯的 ROMP 非常有效。最活跃的物质将 IPr 或 SIPr 作为至少一个 NHC 配体,突出了大体积的异丙基取代基如何增强 NHC 的不稳定性。除了在 UV-C 引发的 ROMP 中的实用性外,这些复合物还对烯基丁腈底物的高温 CM 和 RCM 显示出有希望的活性。
更新日期:2025-03-23
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