{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Rummelt SM"],"funding":["National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["5928-5936"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8293301"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["143(15)"],"pubmed_abstract":["The two-electron oxidative addition of aryl and alkyl halides to a reduced iron dinitrogen complex with a strong-field tridentate pincer ligand has been demonstrated. Addition of iodobenzene or bromobenzene to (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(N<sub>2</sub>)<sub>2</sub> (3,5-Me<sub>2</sub><sup>Mes</sup>CNC = 2,6-(2,4,6-Me-C<sub>6</sub>H<sub>2</sub>-imidazol-2-ylidene)<sub>2</sub>-3,5-Me<sub>2</sub>-pyridine) resulted in rapid oxidative addition and formation of the diamagnetic, octahedral Fe(II) products (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(Ph)(N<sub>2</sub>)(X), where X = I or Br. Competition experiments established the relative rate of oxidative addition of aryl halides as I > Br > Cl. A linear free energy of relative reaction rates of electronically differentiated aryl bromides (ρ = 1.5) was consistent with a concerted-type pathway. The oxidative addition of alkyl halides such as methyl-, isobutyl-, or neopentyl halides was also rapid at room temperature, but substrates with more accessible β-hydrogen positions (e.g., 1-bromobutane) underwent subsequent β-hydride elimination. Cyclization of an alkyl halide containing a radical clock and epimerization of neohexyl iodide-<i>d</i><sub>2</sub> upon oxidative addition to (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(N<sub>2</sub>)<sub>2</sub> are consistent with radical intermediates during C(sp<sup>3</sup>)-X bond cleavage. Importantly, while C(sp<sup>2</sup>)-X and C(sp<sup>3</sup>)-X oxidative addition produces net two-electron chemistry, the preferred pathway for obtaining the products is concerted and stepwise, respectively."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Oxidative Addition of Aryl and Alkyl Halides to a Reduced Iron Pincer Complex."],"pmcid":["PMC8293301"],"funding_grant_id":["R01 GM121441"],"pubmed_authors":["Rummelt SM","Peterson PO","Chirik PJ","Zhong H"],"additional_accession":[]},"is_claimable":false,"name":"Oxidative Addition of Aryl and Alkyl Halides to a Reduced Iron Pincer Complex.","description":"The two-electron oxidative addition of aryl and alkyl halides to a reduced iron dinitrogen complex with a strong-field tridentate pincer ligand has been demonstrated. Addition of iodobenzene or bromobenzene to (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(N<sub>2</sub>)<sub>2</sub> (3,5-Me<sub>2</sub><sup>Mes</sup>CNC = 2,6-(2,4,6-Me-C<sub>6</sub>H<sub>2</sub>-imidazol-2-ylidene)<sub>2</sub>-3,5-Me<sub>2</sub>-pyridine) resulted in rapid oxidative addition and formation of the diamagnetic, octahedral Fe(II) products (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(Ph)(N<sub>2</sub>)(X), where X = I or Br. Competition experiments established the relative rate of oxidative addition of aryl halides as I > Br > Cl. A linear free energy of relative reaction rates of electronically differentiated aryl bromides (ρ = 1.5) was consistent with a concerted-type pathway. The oxidative addition of alkyl halides such as methyl-, isobutyl-, or neopentyl halides was also rapid at room temperature, but substrates with more accessible β-hydrogen positions (e.g., 1-bromobutane) underwent subsequent β-hydride elimination. Cyclization of an alkyl halide containing a radical clock and epimerization of neohexyl iodide-<i>d</i><sub>2</sub> upon oxidative addition to (3,5-Me<sub>2</sub><sup>Mes</sup>CNC)Fe(N<sub>2</sub>)<sub>2</sub> are consistent with radical intermediates during C(sp<sup>3</sup>)-X bond cleavage. Importantly, while C(sp<sup>2</sup>)-X and C(sp<sup>3</sup>)-X oxidative addition produces net two-electron chemistry, the preferred pathway for obtaining the products is concerted and stepwise, respectively.","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Apr","modification":"2025-04-04T20:15:13.151Z","creation":"2025-04-04T20:15:13.151Z"},"accession":"S-EPMC8293301","cross_references":{"pubmed":["33829769"],"doi":["10.1021/jacs.1c01486"]}}