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Issue 86, 2016, Issue in Progress
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Binuclear iron carbonyl complexes of thialene

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Abstract

Thialene (C8H6S) is an isomer of benzothiophene and related to azulene by replacement of a C[double bond, length as m-dash]C unit in the seven-membered ring by a sulfur atom. The geometries of binuclear iron carbonyl complexes of thialene (C8H6S)Fe2(CO)n (n = 6, 5, 4) have been investigated using density functional theory for comparison with the corresponding azulene derivatives. The lowest energy (thialene)Fe2(CO)6 structures have a bis(tetrahapto)-η44-thialene ligand bonded to two separate Fe(CO)3 units without involvement of the sulfur atom. This differs from the isomeric (benzothiophene)Fe2(CO)6 structure known experimentally in which an iron atom has inserted into a carbon–sulfur bond to give a ferrathianaphthalene system. The only low-energy (thialene)Fe2(CO)5 structure has a pentahapto-trihapto-η53 thialene ligand bonded to an Fe2(CO)5 unit, again without involvement of the sulfur atom. This structure is related to the experimental structure of azulene diiron pentacarbonyl, (η53-C10H8)Fe2(CO)5 by replacement of the uncomplexed C[double bond, length as m-dash]C double bond in the seven-membered ring with the sulfur atom in the thialene six-membered ring. The potential energy surface of the unsaturated (thialene)Fe2(CO)4 is very complicated but does not include any low-energy structures with formal Fe[double bond, length as m-dash]Fe double bonds. Thermochemical considerations suggest (thialene)Fe2(CO)5 as a realistic synthetic objective, which is potentially accessible from reactions of thialene with Fe2(CO)9 or (benzalacetone)Fe(CO)3 under mild conditions.

Graphical abstract: Binuclear iron carbonyl complexes of thialene

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Publication details

The article was received on 03 Jun 2016, accepted on 12 Aug 2016 and first published on 16 Aug 2016


Article type: Paper
DOI: 10.1039/C6RA14458F
Citation: RSC Adv., 2016,6, 82661-82668
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    Binuclear iron carbonyl complexes of thialene

    R. Jin, X. Chen, Q. Du, H. Feng, Y. Xie, R. B. King and H. F. Schaefer, RSC Adv., 2016, 6, 82661
    DOI: 10.1039/C6RA14458F

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