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 journalArticle

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

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Thiophenes
Hydrodesulfurization
Thiophene
Alkenes
Olefins
Selenium
Butadiene
Hydrogen
Ligands
Molecules
benzothiophene

ASJC Scopus subject areas

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

Cite this

Reactivity of Mo(PMe3)6 towards benzothiophene and selenophenes : New pathways relevant to hydrodesulfurization. / Buccella, Daniela; Janak, Kevin E.; Parkin, Gerard.

In: Journal of the American Chemical Society, Vol. 130, No. 48, 03.12.2008, p. 16187-16189.

Research output: Contribution to journalArticle

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title = "Reactivity of Mo(PMe3)6 towards benzothiophene and selenophenes: New pathways relevant to hydrodesulfurization",
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, (κ1,η2-CH2CHC6H4S)Mo(PMe3)3(η2-CH2PMe2) and (κ1,η2-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)2(η2-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 (κ1,η2-CH2CC6H4Se)Mo(PMe3)4 and (κ1,η2-CH2CHC6H4Se)Mo(PMe3)3(η2-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 [κ2,η4-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].",
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AU - Buccella, Daniela

AU - Janak, Kevin E.

AU - Parkin, Gerard

PY - 2008/12/3

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N2 - 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, (κ1,η2-CH2CHC6H4S)Mo(PMe3)3(η2-CH2PMe2) and (κ1,η2-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)2(η2-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 (κ1,η2-CH2CC6H4Se)Mo(PMe3)4 and (κ1,η2-CH2CHC6H4Se)Mo(PMe3)3(η2-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 [κ2,η4-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].

AB - 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, (κ1,η2-CH2CHC6H4S)Mo(PMe3)3(η2-CH2PMe2) and (κ1,η2-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)2(η2-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 (κ1,η2-CH2CC6H4Se)Mo(PMe3)4 and (κ1,η2-CH2CHC6H4Se)Mo(PMe3)3(η2-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 [κ2,η4-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].

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