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oai:figshare.com:article/34025291 2026-09-29T17:05:42Z category_1 category_4 category_7 category_8 category_12 category_14 category_272 category_873 category_45 category_734 portal_63 item_type_6 month_year_09_2026

Catalytic Alkene Hydrosilylation and Dinitrogen Silylation by Bis(silylene) and Bis(diphenylphosphino) Cobalt Chlorides Xiaomiao Li (296609) Lin Wang (11986) Shengyong Li (8468007) Qingshuang Li (14205172) Hongjian Sun (1496059) Xiangxu Zhang (22812609) Xiaoyan Li (117291) Biophysics Biochemistry Medicine Microbiology Cell Biology Molecular Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Sociology Biological Sciences not elsewhere classified underwent oxidative addition mechanistic studies confirmed highest value reported exhibited superior activity delivering excellent reactivity bridging methylene group bridging methylene c dinitrogen silylation relative catalyzed dinitrogen silylation l1 </ b 4 </ b 3 </ sub 2 </ sub 1 </ b active cobalt species catalytic alkene hydrosilylation cobalt chlorides three dinitrogen silylation alkene hydrosilylation catalytic performance stoichiometric c olefin hydrosilylation initial c turnover number stoichiometric reductant result indicates mild conditions ligand exchange Three [SiC(sp³)Si]-pincer ligands (<b>L1</b>–<b>L3</b>) and three [PC(sp³)P]-pincer ligands (<b>L4</b>–<b>L6</b>) were reacted with CoCl(PMe₃)₃ to evaluate how silylene and phosphine coordination groups influence both stoichiometric C(sp³)–H activation behavior and catalytic performance in olefin hydrosilylation and dinitrogen silylation. Notably, the [SiCH₂Si]-pincer ligand <b>L1</b> underwent oxidative addition into a bridging methylene C(sp³)–H bond upon reaction with CoCl(PMe₃)₃, yielding a cobalt(III) hydride complex (<b>1</b>); in contrast, the [PC(sp³)P]-pincer ligand <b>L4</b>bearing the identical dipyrromethene scaffoldunderwent only ligand exchange to afford a cobalt(I) chloride complex (<b>4</b>). In catalysis, complex <b>1</b> proved most effective for alkene hydrosilylation, operating under mild conditions and delivering excellent reactivity and regioselectivity. Mechanistic studies confirmed that initial C(sp³)–H activation at the bridging methylene group is crucial for generating the active cobalt species and thereby enabling high catalytic efficiency. Conversely, complex <b>4</b> exhibited superior activity in dinitrogen silylation relative to bis(silylene)-supported cobalt complexes. Critically, this catalytic reaction achieves N₂ activation with a turnover number (TON) of 1228 equiv using lithium metal as a stoichiometric reductant, which is the highest value reported to date for cobalt-catalyzed dinitrogen silylation. This result indicates that the [PC(sp³)P] pincer ligand framework enables more effective dinitrogen silylation compared to the [SiC(sp³)Si] analogue. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/acs.inorgchem.6c03171.s001 https://figshare.com/articles/journal_contribution/Catalytic_Alkene_Hydrosilylation_and_Dinitrogen_Silylation_by_Bis_silylene_and_Bis_diphenylphosphino_Cobalt_Chlorides/34025291 CC BY-NC 4.0