Nicolas G.-Simonian, Mæ Féo, Clément Tanguy, Claire Troufflard, Guillaume Lefèvre
{"title":"Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands","authors":"Nicolas G.-Simonian, Mæ Féo, Clément Tanguy, Claire Troufflard, Guillaume Lefèvre","doi":"10.1021/acscatal.4c03153","DOIUrl":null,"url":null,"abstract":"The field of iron catalysis often faces hurdles in accommodating its transient and unstable low-valent intermediates. By harnessing the noninnocent character of commercial bathocuproine ligand, we managed to develop a reliable functionalization of alkynes with primary, secondary, and tertiary silanes but also with germanium hydrides, catalyzed by a low-valent iron complex. The robustness of the catalyst enabled gram-scale synthesis of vinylsilanes, low catalytic loading, one-pot, hetero, bis-hydrosilylation, but also high steric build-up. Mechanistic studies suggest an important effect of the Mg<sup>II</sup> cation resulting from the reduction of the precatalyst, by assisting the dynamic generation of a highly reactive, under-coordinated iron species from a stable complex.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.4c03153","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The field of iron catalysis often faces hurdles in accommodating its transient and unstable low-valent intermediates. By harnessing the noninnocent character of commercial bathocuproine ligand, we managed to develop a reliable functionalization of alkynes with primary, secondary, and tertiary silanes but also with germanium hydrides, catalyzed by a low-valent iron complex. The robustness of the catalyst enabled gram-scale synthesis of vinylsilanes, low catalytic loading, one-pot, hetero, bis-hydrosilylation, but also high steric build-up. Mechanistic studies suggest an important effect of the MgII cation resulting from the reduction of the precatalyst, by assisting the dynamic generation of a highly reactive, under-coordinated iron species from a stable complex.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.