Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, SAR, Hong Kong, China.
HKUST Shenzhen Research Institute, Shenzhen, 518057, China.
J Am Chem Soc. 2022 Jul 20;144(28):12546-12566. doi: 10.1021/jacs.2c01192. Epub 2022 Jul 6.
Transition metals form a variety of alkylidyne complexes with either a d metal center (high-valent) or a non-d metal center (low-valent). One of the most interesting properties of alkylidyne complexes is that they can undergo or mediate metathesis reactions. The most well-studied metathesis reactions are alkyne metathesis involving high-valent alkylidynes. High-valent alkylidynes can also undergo metathesis reactions with heterotriple bonded species such as N≡CR, P≡CR, and N≡NR. Metathesis reactions involving low-valent alkylidynes are less known. Highly efficient alkyne metathesis catalysts have been developed based on Mo(VI) and W(VI) alkylidynes. Catalytic cross-metathesis of nitriles with alkynes has also been achieved with M(VI) (M = W, Mo) alkylidyne or nitrido complexes. The metathesis activity of alkylidyne complexes is sensitively dependent on metals, supporting ligands and substituents of alkylidynes. Beyond metathesis, metal alkylidynes can also promote other reactions including alkyne polymerization. The remaining shortcomings and opportunities in the field are assessed.
过渡金属与 d 金属中心（高价）或非 d 金属中心（低价）形成各种炔烃络合物。炔烃络合物最有趣的性质之一是它们可以经历或介导复分解反应。研究最多的复分解反应是涉及高价炔烃的炔烃复分解。高价炔烃也可以与杂三键物种如 N≡CR、P≡CR 和 N≡NR 经历复分解反应。涉及低价炔烃的复分解反应则知之甚少。基于 Mo(VI)和 W(VI)炔烃已经开发出高效的炔烃复分解催化剂。M(VI)（M=W、Mo）炔烃或亚氮络合物也实现了腈与炔烃的催化交叉复分解。炔烃络合物的复分解活性对金属、支撑配体和炔烃的取代基非常敏感。除了复分解反应外，金属炔烃还可以促进包括炔烃聚合在内的其他反应。评估了该领域的剩余缺点和机会。
