Preparation and structure of [Cr([eta][sup 6]-C[sub 8]H[sub 6]S)(CO)[sub 3]]. The first transition metal complex of benzo[3,4-c]thiophene

Journal Article · Wed Jul 14 00:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00067a085· OSTI ID:5712949

Selegue, J P; Swarat, K A ^[1]

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1. Univ. of Kentucky, Lexington (United States)

Much of the study on thiophenes has been motivated by the desire to model essential steps of the metal-catalyzed hydrodesulfurization of fossil fuels. Because much of the [open quotes]organic sulfur[close quotes] in fossil fuels is contained in benzo[2,3-b]thiophene and dibenzothiophene groupings, the coordination chemistry of these thiophenes has received considerable attention. In contrast, the coordination chemistry of the nonclassical thiophenes (for which all singlet, uncharged resonance forms invoke C-S double bonding) and benzo[3,4-c]thiophene (1, [open quotes]isothianaphthene[close quotes]) is completely undeveloped. Benzo[c]thiophene (1) is prepared by the dehydration of dihydrobenzo[c]thiophene oxide on alumina. Traces of Lewis acids promote its rapid polymerization to [open quotes]poly-(dihydroisothianaphthene)[close quotes] with a saturated backbone, which can be readily dehydrogenated to [open quotes]poly(isothianaphthene)[close quotes] (PITN). Oxidatively doped PITN is an optically transparent, electrochromic polymer of considerable technological interest, having an amazingly small energy gap (approximately 1 eV) and an electrical conductivity up to approximately 50 [Omega][sup [minus]1] cm[sup [minus]1]. These properties piqued our interest in the synthesis and behavior of transition metal complexes with benzo[3,4-c]thiophene and nonclassical thiophenes as ligands. The reaction of benzo[3,4-c]thiophene with photolytically generated [Cr(thf)(CO)[sub 5]] at room temperature leads to [Cr-(C[sub 8]H[sub 6]/S) (CO)[sub 3]] (2) in up to 62% yield. 34 refs.

• DOE Contract Number: FG05-85ER13432
• OSTI ID: 5712949
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 115:14; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHROMIUM COMPLEXES
MOLECULAR STRUCTURE
SYNTHESIS
FOSSIL FUELS
DESULFURIZATION
CRYSTALLOGRAPHY
NUCLEAR MAGNETIC RESONANCE
THIONAPHTHENES
CHEMICAL REACTIONS
COMPLEXES
ENERGY SOURCES
FUELS
HETEROCYCLIC COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RESONANCE
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures