Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+

Kenji Itoh, Katsuyuki Masuda, Takahiko Fukahori, Katsumasa Nakano, Katsuyuki Aoki, Hideo Nagashima

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Abstract

When Cp*Ru(η4-butadiene)X (Cp* = η5-C5Me5; 1a, X = Cl; 1b, X = Br) was treated with excess butadiene in the presence of silver trifluoromethanesulfonate (AgOTf) followed by carbon monoxide (1 atm), 1,5-cyclooctadiene complex [Cp*Ru(η22-C8H12)(CO)]OTf (2) was isolated in 79% yield. Similar [4 + 4] cycloaddition occurred in the reaction of Cp*Ru(η4-isoprene)Cl (1c) with isoprene, AgOTf, and CO to give [Cp*Ru(η22-cis-3,7-dimethyl-1,5-cyclooctadiene)-(CO)]OTf (4a) at ambient temperature. Similar reaction of Cp*Ru(η4-1,3-pentadiene)Cl (1d) with 1,3-pentadiene, however, furnished [Cp*Ru(4-methyl-(1,3-η3:6–8-η3)-nonadienediyl)]OTf (5) in the presence of AgOTf as result of regiospecific linear dimerization. This stoichiometric regioselective dimerization was extended to catalytic formation of 1,5-cyclooctadiene, dimethylcyclooctadienes, and 6-methyl-2,4,7-nonatriene from butadiene, isoprene, or 1,3-pentadiene, respectively, with a catalytic amount of 1b, 1c, or 1d and AgOTf. Alternatively, treatment of butadiene with CpRu(η4-butadiene)Br (Cp = η5-C5H5) and AgOTf induced linear dimerization of butadiene, and [CpRu(η42-1,3,7-octatriene)]OTf (6) was obtained in 98% yield by way of single-step C–C bond formation.

Original languageEnglish
Pages (from-to)1020-1029
Number of pages10
JournalOrganometallics
Volume13
Issue number3
DOIs
Publication statusPublished - Mar 1 1994
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Itoh, K., Masuda, K., Fukahori, T., Nakano, K., Aoki, K., & Nagashima, H. (1994). Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C5R5)Ru(diene)+. Organometallics, 13(3), 1020-1029. https://doi.org/10.1021/om00015a040