Properties and Catalytic Activity of Hoveyda–Grubbs-Type Catalysts with an S → Ru Coordination Bond in a Six-Membered Chelate Ring,Organometallics

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Properties and Catalytic Activity of Hoveyda–Grubbs-Type Catalysts with an S → Ru Coordination Bond in a Six-Membered Chelate Ring
Organometallics ( IF 2.5 ) Pub Date : 2023-01-27 , DOI: 10.1021/acs.organomet.2c00556
Pavel A. Kumandin ₁ , Alexandra S. Antonova ₁ , Roman A. Novikov ₂ , Kirill A. Vasilyev ₁ , Marina A. Vinokurova ₁ , Mikhail S. Grigoriev ₃ , Anton P. Novikov ₃ , Daria K. Polianskaia ₁ , Kirill B. Polyanskii ₁ , Fedor I. Zubkov ₁

Affiliation

This work continues our group’s research into the synthesis and study of the catalytic activity of ruthenium chelates with various heteroatoms (O, S, N, and Se) in a six-membered ring. It was found that second-generation Hoveyda–Grubbs-type catalysts containing a sulfur-ruthenium coordinate bond in a six-membered chelate ring can be prepared easily and in high yields using standard procedures, based on the interaction between (2-vinylbenzyl)sulfanes and Ind II (the common precursor for Ru-complex synthesis). The obtained ruthenium derivatives, with a donor-acceptor S → Ru bond, can exist in two isomeric forms according to the arrangement of substituents around the central metal atom. Kinetically controlled trans-isomers are formed at temperatures below 80 °C in heptane and are less thermodynamically stable compared with cis-isomers, which arise under heating of trans-S-chelates in 1,2-dichloroethane at 110 °C. The structures of all the cis- and trans-isomers were determined and characterized in detail by X-ray diffraction and nuclear magnetic resonance. The study of the activity of the catalysts in standard ring-closing metathesis and ring-opening metathesis polymerization reactions showed that the cis-isomers are inactive in the absence of thermal or UV activation, while trans-complexes of the same type display excellent catalytic properties at r.t. that are superior to those of the commercially available HG-II catalyst. The structure, spectral characteristics, and catalytic activity of the catalysts containing an S → Ru bond in a six-membered chelate ring were compared with their five-membered analogues obtained in previous works.

中文翻译：

六元螯合环中 S→Ru 配位键的 Hoveyda–Grubbs 型催化剂的性质和催化活性

这项工作延续了我们小组对六元环中具有各种杂原子（O、S、N 和 Se）的钌螯合物的合成和催化活性研究的研究。人们发现，基于 (2-乙烯基苄基) 硫烷之间的相互作用，可以使用标准程序轻松且高收率地制备在六元螯合环中含有硫-钌配位键的第二代 Hoveyda–Grubbs 型催化剂和Ind II（Ru 配合物合成的常见前体）。所得钌衍生物具有供体-受体S →Ru键，根据中心金属原子周围取代基的排列可以存在两种异构形式。动力学控制反式异构体在低于 80 °C的温度下在庚烷中形成，并且与顺式异构体相比热力学稳定性较低，顺式异构体是在 1,2-二氯乙烷中的反式-S-螯合物在 110 °C 下加热时产生的。所有顺式和反式异构体的结构都通过 X 射线衍射和核磁共振进行了详细测定和表征。对标准闭环复分解和开环复分解聚合反应中催化剂活性的研究表明，顺式异构体在没有热或紫外线活化的情况下是无活性的，而反式- 相同类型的配合物在室温下显示出优于市售 HG-II 催化剂的优异催化性能。将六元螯合环中含有S →Ru 键的催化剂的结构、光谱特征和催化活性与之前工作中获得的五元类似物进行了比较。

更新日期：2023-01-27

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