C-H bond activation of benzene and thiophene by photochemically generated rhenocene cation

Hiroshi Ogino, Hiromi Tobita, Kouji Endo, Kiyonari Hashidzume

Research output: Contribution to journalArticle

Abstract

A cationic rhenocene-acetonitrile adduct [Cp2Re(NCMe)](BF4)(1) reacted with an excess of benzene, thiophene, 2-methylthiophene, and pyrrole under UV irradiation to afford the C - H bond activation products [Cp2Re(H)R]BF4 (R = phenyl, 2-thienyl, 2-(5-methylthienyl), 2-pyrrolyl) in high yields. In cases of thiophene derivatives and pyrrole, α-C - H bonds are selectively activated. A plausible mechanism involves the photodissociation of acetonitrile from 1 to generate a coordinatively unsaturated rhenocene cation [Cp2Re]+. When 2,5-dimethylthiophene and dibenzothiophene, having no α-C - H bonds, were used as substrates, products of the activation of other C - H bonds were formed first, but they isomerized to thermodynamically more stable η1-S-coordinated complexes in refluxing acetone. On the other hand, irradiation of the η1-S-coordinated complexes reproduced the original C - H bond activation products. Because of the cationic character, [Cp2Re(H)R]BF4 were readily deprotonated by triethylamine to give neutral rhenocene derivatives Cp2ReR. When R is thienyl or 2-(5-methylthienyl), treatment of Cp2ReR with HBF4 · Et2O and MeI resulted in protonation and methylation to give [Cp2Re(H)R]BF4 and [Cp2Re(Me)R]I. Thermolysis of [Cp2Re(Me)R]I in the presence of PPh3 unexpectedly resulted in migration of R to the Cp ring to give [(2-thienyl C5H4) CpRe (PPh3)]I.

Original languageEnglish
JournalInternational Journal of Photoenergy
Volume1
Issue number3
Publication statusPublished - 1999 Dec 1

ASJC Scopus subject areas

  • Chemistry(all)
  • Atomic and Molecular Physics, and Optics
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

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