title: Electronic structure of monodithiolated iron-oxotungsten heterometallic complexes: integer-spin Fe-W assembly.
abstract: Fe-W heterometallic complexes, in which an FeX2 (X = Cl, SPh) moiety is attached to monodithiolene oxotungsten through a sulfide bridge, that is, [Ph4P]2[Cl2Fe(S)2WOS2] (1), [Ph4P]2[Cl2Fe(S)2WOS2(DMED)] (2, DMED = dimethylethylenedicarboxylate), [Ph4P]2[Cl2Fe(S)2WO(tdt)] (3, tdt = toluenedithiolate), [Ph4P]2[(SPh)2Fe(S)2WO(tdt)] (4), and [Ph4P]2[Cl2Fe(S)2WO(edt)] (5, edt = ethanedithiolate), are reported. Mössbauer and EPR spectroscopy, magnetism, electrochemistry, and electronic structural analysis based on DFT and TD-DFT calculations show the transfer of electron from the iron center to the tungsten center, thus resulting in a ferromagnetically coupled Fe(III) W(V) unit, along with antiferromagnetic intermolecular interactions, from the starting Fe(II) and W(VI) compounds. A net spin of a S = 3 ground state, which arises from ferromagnetically coupled Fe(III) and W(V) atoms, displays a rare X-band EPR in normal mode at g ≈ 7 in the solid state.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kanpur, Kanpur-208016, Uttar Pradesh, India.
authors.forename: Moumita
authors.initials: M
authors.lastname: Bose
authors.forename: Golam
authors.initials: G
authors.lastname: Moula
authors.forename: Sabyasachi
authors.initials: S
authors.lastname: Sarkar
mesh_terms: D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction; D004579:Electron Transport; D007501:Iron / Q000737:chemistry*; D008280:Magnetics; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015204:Spectroscopy, Mossbauer; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D007501:Iron; D014414:Tungsten