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Redox Processes Involved in the Synthesis and Reactivity of Oxazolinylthiophenolato Complexes of Iron(II)/(III)
Author(s) -
Bottini Rúbia C. R.,
Gariani Rogério A.,
Cavalcanti César de O.,
de Oliveira Franciele,
da Rocha Nevilde de L. G.,
Back Davi,
Lang Ernesto S.,
Hitchcock Peter B.,
Evans David J.,
Nunes Giovana G.,
Simonelli Fábio,
de Sá Eduardo L.,
Soares Jaísa F.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000065
Subject(s) - chemistry , redox , anhydrous , cyclic voltammetry , reactivity (psychology) , ligand (biochemistry) , mössbauer spectroscopy , transition metal , metal , crystallography , electrochemistry , inorganic chemistry , medicinal chemistry , catalysis , organic chemistry , medicine , biochemistry , alternative medicine , receptor , electrode , pathology
The reaction of anhydrous FeCl 2 with 2‐(4′,4′‐dimethyloxazolin‐2′‐yl)thiophenolate (ox‐phS – ) afforded mononuclear [Fe(ox‐phS) 2 ] ( A ) and binuclear [{Fe III (ox‐phS)} 2 (μ‐S) 2 ] ( B ). In B , iron(III) and S 2– resulted from an unexpected redox reaction involving elemental sulfur and the iron(II) starting material. Complexes A and B co‐crystallise reproducibly in a 2:1 proportion. An attempt to prepare (oxazolinylthiophenolato)iron(III) from Li(ox‐phS) and anhydrous FeCl 3 in the presence of N , N , N′ , N′ ‐tetramethylethane‐1,2‐diamine (tmen) gave another redox reaction with disulfide D , bis{2‐(4′,4′‐dimethyloxazolin‐2′‐yl)phenyl}disulfide (ox‐phS‐Sph‐ox), and trans ‐[FeCl 2 (tmen) 2 ] ( E ) as 1:1 co‐crystallised products. Characterisation of all complexes included Mössbauer spectroscopy and single‐crystal X‐ray diffraction analysis. Quantum mechanical (TDDFT) calculations for A and cyclic voltammetry experiments carried out with A and C helped to distinguish between ligand‐ and metal‐based electronic transitions and redox processes. Results add to the knowledge of the rich redox chemistry of early transition metals with soft S‐donor ligands, with possible consequences for catalytic and biochemical transformations.