Electronic Structure of Monodithiolated IronOxotungsten Heterometallic Complexes: Integer‐Spin FeW Assembly. Issue 6 (15th April 2013)

• Record Type: Journal Article
• Authors: Bose, Moumita; Moula, Golam; Sarkar, Sabyasachi
• Is Part Of: Chemistry, an Asian journal. Volume 8:Issue 6(2013:Jun.)
• Page Start: 1128
• Page End: 1138
• Publication Date: 2013-04-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201300245
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>FeW heterometallic complexes, in which an FeX<sub>2</sub> (X=Cl, SPh) moiety is attached to monodithiolene oxotungsten through a sulfide bridge, that is, [Ph<sub>4</sub>P]<sub>2</sub>[Cl<sub>2</sub>Fe(S)<sub>2</sub>WOS<sub>2</sub>] (<xref ref-type="link" rid="sch1">1</xref>), [Ph<sub>4</sub>P]<sub>2</sub>[Cl<sub>2</sub>Fe(S)<sub>2</sub>WOS<sub>2</sub>(DMED)] (<xref ref-type="link" rid="sch1">1</xref>, DMED=dimethylethylenedicarboxylate), [Ph<sub>4</sub>P]<sub>2</sub>[Cl<sub>2</sub>Fe(S)<sub>2</sub>WO(tdt)] (<xref ref-type="link" rid="sch1">1</xref>, tdt=toluenedithiolate), [Ph<sub>4</sub>P]<sub>2</sub>[(SPh)<sub>2</sub>Fe(S)<sub>2</sub>WO(tdt)] (<xref ref-type="link" rid="sch1">1</xref>), and [Ph<sub>4</sub>P]<sub>2</sub>[Cl<sub>2</sub>Fe(S)<sub>2</sub>WO(edt)] (<xref ref-type="link" rid="sch1">1</xref>, 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<sup>III</sup>W<sup>V</sup> unit, along with antiferromagnetic intermolecular interactions, from the starting Fe<sup>II</sup> and W<sup>VI</sup> compounds. A net spin of a <italic>S</italic>=3 ground state, which arises from ferromagnetically coupled Fe<sup>III</sup> and W<sup>V</sup> atoms, displays a rare X‐band EPR in normal mode at <italic>g</italic>≈7 in the solid state.</p> </abstract>