112440-08-1Relevant articles and documents
Redox processes involved in the synthesis and reactivity of oxazolimlthiophenolato complexes of iron(II)/(III)
Bottini, Rubia C. R.,Gariani, Rogerio A.,De Cavalcanti, Cesar O.,De Oliveira, Franciele,De Da Rocha, Nevilde L. G.,Back, Davi,Lang, Ernesto S.,Hitchcock, Peter B.,Evans, David J.,Nunes, Giovana G.,Simonelli, Fabio,De Sa, Eduardo L.,Soares, Jaisa F.
, p. 2476 - 2487 (2010/10/01)
The reaction of anhydrous FeCl2 with 2-(4′,4′- dimethyloxazolin-2′-yl)thiophenolate (ox-phS-) afforded mononuclear [Fe(ox-phS)2] (A) and binuclear [[FeIII(ox- phS)}2(μ-S)2] (B). In B, iron(III) and S2- 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 FeCl3 in the presence of N,N,N′,N -tetramethyletha:n.e-1,2-diamine (tmen) gave another redox reaction with disulfide D, bis{2-(4′,4′-di-methyloxazolln-2′-yl)phenyl} disulfide (ox-phS-Sph-ox), and trans-[FeCl2(tmen)2] (E) as 1:1 co-crystallised products. Characterisation of all complexes included Moessbauer 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.
