Oxidation state characterization of ruthenium 2 - Lminoquinone complexes through experimental and theoretical studies

Jonathan Rochford, Ming Kang Tsai, David J. Szalda, Julie L. Boyer, James T. Muckerman, Etsuko Fujita

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Abstract

The synthesis of complexes [RuIItrpy)(2-imino-4-tert- butylquinone)(Cl)]+ and [Ru11(trpy)(NIL)(OAc)]+ (where trpy = 2:2′,6′:2″-terpyridyl, NIL = 2-imino-4-tert-butylquinone, 2-imino-4-methylquinone, 2-iminoquinone, 2-imino-4-chloroquinone, 2-imino-5-chloroquinone, 2-imino-4,6-di-tert-butyl-N- phenyl-quinone, 2-imino-4,6-di-tert-butyl-N-(2′-trifluoromethylphenyl)- quinone) is reported. The oxidation states of these complexes, as well as the previously reported [Ru111(trpy)(2-iminosemiquinone)(Cl)]+ complex, are investigated by spectroscopic, electrochemical and theoretical methods resulting in the latter complex being reassigned as [Ru II(trpy)(2-iminoquinone)(Cl)]+. Evidence for the presence of two structural isomers was found for all complexes, and crystal structures for both isomers of the [RuII(trpy)(2-imino-4-tetr-butylquinone)(Cl)] ClO4 complex are reported, as well as for the cis isomer of [Ru II(trpy)(2-imino-4,6-di-tert-butyl-N-phenyl-quinone)(OAc)]PF 6. Redox control is also demonstrated based on the Hammett parameters of the substituents on the 2-iminoquinone ligand.

Original languageEnglish
Pages (from-to)860-869
Number of pages10
JournalInorganic Chemistry
Volume49
Issue number3
DOIs
Publication statusPublished - Feb 1 2010

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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