C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes

Sumito Ishizu, Hiroyasu Sugiyama, Brian K. Breedlove, Kazuko Matsumoto

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(μ- S2)(μ-X)2{μ-m-C6H4(CH 2CN)2}]-(CF3SO3)2 (4, X = Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2- (μ-S 2)(μ-X)2] (1, X = Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C 4S2 ring-bridged complex [{Ru(P(OCH3) 3)2}2{μ-SCH2C(CH 3)=C(CH3)CH2S}(μ-X)2{μ-m- C6H4(CH2-CN)2}](CF 3SO3)2 (6, X = Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{μ-SS(CH 2C=CHR)}(μ-Cl)2-{μ-m-C6H 4(CH2CN)2}](CF3SO3) (7: R = CH2CH3, 9: R = CH2-CH2CH 3) and alkenyl methyl disulfide complexes [{Ru(P(OCH 3)3)2}2{μ-S(CH 3)S(CH2C=HR)}(μ-Cl)2{μ-m-C 6H4(CH2-CN)2}](CF3SO 3)2 (8: R = CH2CH3,10: R = CH 2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH 3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru-(P(OCH3)3)2}2{μ-SS(CH 2C=CHCH2OH)}(μ-Cl)2{μ-m-C 6H4(CH2CN)2}](CF3SO 3) (11) via the elimination of H+ and [{Ru(P(OCH 3)3)2}2(μ-SCH2CH= CHCH2S)(μ-Cl)2{μ-m-C6H 4(CH2CN)2}](CF3SO3) 2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.

Original languageEnglish
Pages (from-to)3726-3735
Number of pages10
JournalInorganic chemistry
Volume46
Issue number9
DOIs
Publication statusPublished - 2007 Apr 30
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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