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• W2239259315 endingPage "572" @default.
• W2239259315 startingPage "566" @default.
• W2239259315 abstract "Two mononuclear nonheme Fe(III) complexes, [PPh4][Fe(III)(PS3″)(OCH3)] (1) and [PPh4][Fe(III)(PS3″)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3″ (PS3″ = P(C6H3-3-Me3Si-2-S)3(3-)) have been synthesized and characterized. The structures resolved from X-ray crystallography show that Fe(III) centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin Fe(III) centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming Fe(III)-CH3CN species can be further reduced by cobaltcene quantitatively to a stable Fe(II)-CH3CN complex, [Fe(PS3″)(CH3CN)](-). One-electron oxidation of 2 by ferrocenium gave a Fe(IV) analogue, [Fe(IV)(PS3″)(Cl)]. Importantly, the Fe(III)-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate Fe(III)-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies." @default.
• W2239259315 created "2016-06-24" @default.
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• W2239259315 date "2015-12-23" @default.
• W2239259315 modified "2023-09-25" @default.
• W2239259315 title "Reactivity of a Fe(III)-Bound Methoxide Supported with a Tris(thiolato)phosphine Ligand: Activation of C–Cl Bond in CH2Cl2 by Nucleophilic Attack of a Fe(III)–OCH3 Moiety" @default.
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• W2239259315 doi "https://doi.org/10.1021/acs.inorgchem.5b02135" @default.
• W2239259315 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/26699874" @default.
• W2239259315 hasPublicationYear "2015" @default.
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