Six-Coordinate Nitrato Complexes of Iron Porphyrins with Trans S‑Donor Ligands

The reaction of dimethyl sulfide (DMS) and tetrahydrothiophene (THT) with thin, amorphous layers of the nitrato complexes Fe­(Por)­(η2-O2NO) (Por = meso-tetraphenylporphyrinato dianion or meso-tetra-p-tolylporphyrinato dianion) at low temperature leads to formation of the corresponding six-coordinat...

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Published inInorganic chemistry Vol. 57; no. 9; pp. 4795 - 4798
Main Authors Kurtikyan, Tigran S, Gulyan, Gurgen M, Minasyan, Hayk S, Hovhannisyan, Astghik A, Ford, Peter C
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 07.05.2018
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Summary:The reaction of dimethyl sulfide (DMS) and tetrahydrothiophene (THT) with thin, amorphous layers of the nitrato complexes Fe­(Por)­(η2-O2NO) (Por = meso-tetraphenylporphyrinato dianion or meso-tetra-p-tolylporphyrinato dianion) at low temperature leads to formation of the corresponding six-coordinate complexes Fe­(Por)­(L)­(η1-ONO2) (L = DMS, THT) as characterized by Fourier transform infrared and optical spectroscopy measurements. Adduct formation was accompanied by bidentate-to-monodentate linkage isomerization of the nitrato ligand, with the FeIII center remaining in a high-spin electronic state. These adducts are thermally unstable; warming to room temperature restores the initial Fe­(Por)­(η2-O2NO) species.
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ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b00253