Reactivity of Mo(PMe3)6 towards benzothiophene and selenophenes: New pathways relevant to hydrodesulfurization

Daniela Buccella, Kevin E. Janak, Gerard Parkin

Research output: Contribution to journalArticlepeer-review

Abstract

Mo(PMe3)6 cleaves a C-S bond of benzothiophene to give (κ2-CHCHC6H4S)Mo(PMe3)4, which rapidly isomerizes to the olefin-thiophenolate and 1-metallacyclopropene-thiophenolate complexes, (κ12-CH2CHC6H4S)Mo(PMe3)32-CH2PMe2) and (κ12-CH2CC6H4S)Mo(PMe3)4. The latter two molecules result from a series of hydrogen transfers and are differentiated according to whether the termini of the organic fragments coordinate as olefin or η2-vinyl ligands, respectively. The reactions between Mo(PMe3)6 and selenophenes proceed differently from those of the corresponding thiophenes. For example, whereas Mo(PMe3)6 reacts with thiophene to give η5-thiophene and butadiene-thiolate complexes, (η5-C4H4S)Mo(PMe3)3 and (η5-C4H5S)Mo(PMe3)22-CH2PMe2), selenophene affords the metallacyclopentadiene complex [(κ2-C4H4)Mo(PMe3)3(Se)]2[Mo(PMe3)4] in which the selenium has been completely abstracted from the selenophene moiety. Likewise, in addition to (κ12-CH2CC6H4Se)Mo(PMe3)4 and (κ12-CH2CHC6H4Se)Mo(PMe3)32-CH2PMe2), which are counterparts of the species observed in the benzothiophene reaction, the reaction of Mo(PMe3)6 with benzoselenophene yields products resulting from C-C coupling, namely [κ24-Se(C6H4)(CH)4(C6H4)Se]Mo(PMe3)2 and [μ-Se(C6H4)(CH)C(CH)2(C6H4)](μ-Se)[Mo(PMe3)2][Mo(PMe3)2H].

Original languageEnglish (US)
Pages (from-to)16187-16189
Number of pages3
JournalJournal of the American Chemical Society
Volume130
Issue number48
DOIs
StatePublished - Dec 3 2008

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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