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单核和双核钼及钨基施罗克催化剂在离子液体中用于两相烯烃复分解反应。

Mono- and Bisionic Mo- and W-Based Schrock Catalysts for Biphasic Olefin Metathesis Reactions in Ionic Liquids.

机构信息

Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany.

XiMo Hungary Kft., Záhony u. 7, H-1031, Budapest, Hungary.

出版信息

Chemistry. 2018 Sep 6;24(50):13336-13347. doi: 10.1002/chem.201802472. Epub 2018 Aug 13.

Abstract

An extensive series of the first ionic Mo- and W-based Schrock-type catalysts based on pyridinium and phosphonium tagged aryloxide ligands were prepared. Bisionic complexes of the general formula Mo(Imido)(CHR)(OR') (OTf) and monoionic monoaryloxide pyrrolide (pyr) (MAP-type) catalysts [M(Imido)(CHR)(OR')(pyr) ][A ] were successfully employed and tested in various olefin metathesis benchmark reactions under both, homogeneous and biphasic conditions using pyrrole and, for the first time with Schrock-type catalysts, ionic liquids as the polar phase. Productivities under biphasic conditions up to several thousand turn overs were achieved and are comparable to those obtained in reactions carried out in chlorobenzene or toluene. Metal contamination in the nonpolar product-containing heptane phase was <2 ppm.

摘要

制备了一系列基于吡啶鎓和鏻标记的芳氧基配体的新型离子型 Mo 和 W 基 Schrock 型催化剂。成功地使用了通式为 Mo(Imido)(CHR)(OR')(OTf) 和单离子单芳氧基亚吡咯烷 (MAP 型) 催化剂 [M(Imido)(CHR)(OR')(pyr)][A] 的双离子配合物,并在均相和两相条件下,使用吡咯以及首次使用 Schrock 型催化剂的离子液体作为极性相,在各种烯烃复分解基准反应中进行了测试。在两相条件下可实现高达数千个转化的产率,与在氯苯或甲苯中进行的反应获得的产率相当。非极性产物相中的金属污染 <2 ppm。

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