Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-08 , DOI: 10.1039/d0sc04402d
Casseday P Richers _{1,

2} , Sven Roediger ₁ , Victor Laserna ₁ , John F Hartwig _{1,

2}

Affiliation

Migratory insertions of olefins into metal–oxygen bonds are elementary steps of important catalytic processes, but well characterised complexes that undergo this reaction are rare, and little information on the effects of ancillary ligands on such reactions has been gained. We report a series of alkoxo alkene complexes of rhodium(I) that contain a range of bidentate ligands and that undergo insertion of the alkene. Our results show that complexes containing less electron-donating ancillary ligands react faster than their counterparts containing more electron-donating ancillary ligands, and that complexes possessing ligands with larger bite angles react faster than those with smaller bite angles. External added ligands had several effects on the reactions, including an inhibition of olefin isomerisation in the product and acceleration of the displacement of the product from complexes of ancillary ligands with small bite angles. Complementary computational studies help elucidate the details of these insertion processes.

中文翻译：

配体对烯烃迁移插入铑-氧键的影响

烯烃迁移插入金属-氧键是重要催化过程的基本步骤，但经历该反应的良好表征的配合物很少见，并且关于辅助配体对此类反应的影响的信息很少。我们报道了一系列铑( I )的烷氧基烯烃配合物，其含有一系列二齿配体并且经历了烯烃的插入。我们的结果表明，含有较少供电子辅助配体的配合物比含有较多供电子辅助配体的配合物反应更快，并且具有较大咬角的配体的配合物比具有较小咬角的配体反应更快。外部添加的配体对反应有多种影响，包括抑制产物中的烯烃异构化和加速产物从具有小咬角的辅助配体复合物中的置换。补充计算研究有助于阐明这些插入过程的细节。

更新日期：2020-10-07

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11