{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Gordon JB"],"funding":["Johns Hopkins University","National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["21637-21647"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9109941"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["143(51)"],"pubmed_abstract":["Addition of dioxygen at low temperature to the non-heme ferrous complex Fe<sup>II</sup>(Me<sub>3</sub>TACN)((OSi<sup>Ph2</sup>)<sub>2</sub>O) (<b>1</b>) in 2-MeTHF produces a peroxo-bridged diferric complex Fe<sub>2</sub><sup>III</sup>(μ-O<sub>2</sub>)(Me<sub>3</sub>TACN)<sub>2</sub>((OSi<sup>Ph2</sup>)<sub>2</sub>O)<sub>2</sub> (<b>2</b>), which was characterized by UV-vis, resonance Raman, and variable field Mössbauer spectroscopies. Illumination of a frozen solution of <b>2</b> in THF with white light leads to homolytic O-O bond cleavage and generation of a Fe<sup>IV</sup>(O) complex <b>4</b> (ν(Fe=O) = 818 cm<sup>-1</sup>; δ = 0.22 mm s<sup>-1</sup>, Δ<i>E</i><sub>Q</sub> = 0.23 mm s<sup>-1</sup>). Variable field Mössbauer spectroscopy measurements show that <b>4</b> is a rare example of a high-spin <i>S</i> = 2 Fe<sup>IV</sup>(O) complex and the first synthetic example to be generated directly from O<sub>2</sub>. Complex <b>4</b> is highly reactive, as expected for a high-spin ferryl, and decays rapidly in fluid solution at cryogenic temperatures. This decay process in 2-MeTHF involves C-H cleavage of the solvent. However, the controlled photolysis of <b>2</b> <i>in situ</i> with visible light and excess phenol substrate leads to competitive phenol oxidation, via the proposed transient generation of <b>4</b> as the active oxidant."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["A Reactive, Photogenerated High-Spin (<i>S</i> = 2) Fe<sup>IV</sup>(O) Complex via O<sub>2</sub> Activation."],"pmcid":["PMC9109941"],"funding_grant_id":["R01 GM119374","R01GM119374"],"pubmed_authors":["Moenne-Loccoz P","Dey A","Bill E","Gordon JB","Albert T","Sabuncu S","Siegler MA","Goldberg DP"],"additional_accession":[]},"is_claimable":false,"name":"A Reactive, Photogenerated High-Spin (<i>S</i> = 2) Fe<sup>IV</sup>(O) Complex via O<sub>2</sub> Activation.","description":"Addition of dioxygen at low temperature to the non-heme ferrous complex Fe<sup>II</sup>(Me<sub>3</sub>TACN)((OSi<sup>Ph2</sup>)<sub>2</sub>O) (<b>1</b>) in 2-MeTHF produces a peroxo-bridged diferric complex Fe<sub>2</sub><sup>III</sup>(μ-O<sub>2</sub>)(Me<sub>3</sub>TACN)<sub>2</sub>((OSi<sup>Ph2</sup>)<sub>2</sub>O)<sub>2</sub> (<b>2</b>), which was characterized by UV-vis, resonance Raman, and variable field Mössbauer spectroscopies. Illumination of a frozen solution of <b>2</b> in THF with white light leads to homolytic O-O bond cleavage and generation of a Fe<sup>IV</sup>(O) complex <b>4</b> (ν(Fe=O) = 818 cm<sup>-1</sup>; δ = 0.22 mm s<sup>-1</sup>, Δ<i>E</i><sub>Q</sub> = 0.23 mm s<sup>-1</sup>). Variable field Mössbauer spectroscopy measurements show that <b>4</b> is a rare example of a high-spin <i>S</i> = 2 Fe<sup>IV</sup>(O) complex and the first synthetic example to be generated directly from O<sub>2</sub>. Complex <b>4</b> is highly reactive, as expected for a high-spin ferryl, and decays rapidly in fluid solution at cryogenic temperatures. This decay process in 2-MeTHF involves C-H cleavage of the solvent. However, the controlled photolysis of <b>2</b> <i>in situ</i> with visible light and excess phenol substrate leads to competitive phenol oxidation, via the proposed transient generation of <b>4</b> as the active oxidant.","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Dec","modification":"2025-04-26T12:06:13.591Z","creation":"2025-04-06T13:52:05.578Z"},"accession":"S-EPMC9109941","cross_references":{"pubmed":["34913683"],"doi":["10.1021/jacs.1c10051"]}}