112440-08-1Relevant academic research and scientific papers
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.
Pentamethylcyclopentadienylbis(ethene)iron - a 17e Halfsandwich Complex with Easily Displaceable Ethene Ligands
Jonas, Klaus,Klusmann, Peter,Goddard, Richard
, p. 394 - 404 (2007/10/02)
The new room temperature stable halfsandwich complex Cp*Fe(tmeda)Cl (2) has been synthesized by the 1:1 reaction of FeCl2(thf)1.5 with LiCp* in a mixture of THF and TMEDA at -30 deg C. 2 is an ideal starting material for the synthesis of a wide range of new iron complexes.Treatment of 2 with lithium sand in THF in the presence of COD are ethene followed by the addition of TMEDA yields the ferrates (3) or (4).By delithiation with dichloroethane, 3 and 4 can be transformed into the novel 17e iron complexes Cp*Fe(cod) (5) and Cp*Fe(C2H4)2 (6). 6 is extremely labile.Since the ethene ligands can be easily displaced, the title compound is a synthetically valuable source of the Cp*Fe fragment.Whereas the photochemically generated 17e dicarbonyl species CpFe(CO)2 rapidly recombines to give the dimer 2, the isoelectronic 6 is stable in ethene saturated pentane for several days at 0 deg C.Without the stabilizing effect of ethene (in pure pentane or under vacuum), 6 loses ethene to give the dinuclear complex (Cp*Fe)2(C2H4)2 (8) irreversibly.The structure of 8 has been characterized by X-ray analysis. - Keywords: Bis(ethene)iron, Halfsandwich, Dinuclear Iron Complex
