Zhai Xiaofang, Xue Minghui, Zhao Qiuting, Zheng Qiucui, Song Datong, Tung Chen-Ho, Wang Wenguang
College of Chemistry, Beijing Normal University, 100875, Beijing, China.
School of Chemistry and Chemical Engineering, Shandong University, 250100, Jinan, China.
Nat Commun. 2024 Sep 4;15(1):7729. doi: 10.1038/s41467-024-52116-9.
Transition metal carbyne complexes are of fundamental importance in carbon-carbon bond formation, alkyne metathesis, and alkyne coupling reactions. Most reported iron carbyne complexes are stabilized by incorporating heteroatoms. Here we show the synthesis of bioinspired FeMo heterobimetallic carbyne complexes by the conversion of CH through a diverse series of intermediates. Key reactions discovered include the reduction of a μ-η:η-CH ligand with a hydride to produce a vinyl ligand (μ-η:η-CH = CH), tautomerization of the vinyl ligand to a carbyne (μ-CCH), and protonation of either the vinyl or the carbyne compound to form a hydrido carbyne heterobimetallic complex. Mechanistic studies unveil the pivotal role of HO as a proton shuttle, facilitating the proton transfer that converts the vinyl group to a bridging carbyne.
过渡金属卡宾配合物在碳-碳键形成、炔烃复分解反应和炔烃偶联反应中具有至关重要的作用。大多数已报道的铁卡宾配合物通过引入杂原子来实现稳定。在此，我们展示了通过一系列不同的中间体将CH进行转化来合成受生物启发的FeMo异双金属卡宾配合物。发现的关键反应包括用氢化物还原μ-η:η-CH配体以生成乙烯基配体(μ-η:η-CH=CH)、乙烯基配体互变异构为卡宾(μ-CCH)以及乙烯基或卡宾化合物的质子化以形成氢化物卡宾异双金属配合物。机理研究揭示了HO作为质子穿梭体的关键作用，促进了将乙烯基转化为桥连卡宾的质子转移。
