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 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

Fingerprint

Ruthenium
quinones
Isomers
ruthenium
isomers
Oxidation
oxidation
Crystal structure
Ligands
ligands
crystal structure
synthesis
iminoquinone
benzoquinone
2-tert-butyl-4-quinone

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Oxidation state characterization of ruthenium 2 - Lminoquinone complexes through experimental and theoretical studies. / Rochford, Jonathan; Tsai, Ming Kang; Szalda, David J.; Boyer, Julie L.; Muckerman, James; Fujita, Etsuko.

In: Inorganic Chemistry, Vol. 49, No. 3, 01.02.2010, p. 860-869.

Research output: Contribution to journalArticle

Rochford, Jonathan ; Tsai, Ming Kang ; Szalda, David J. ; Boyer, Julie L. ; Muckerman, James ; Fujita, Etsuko. / Oxidation state characterization of ruthenium 2 - Lminoquinone complexes through experimental and theoretical studies. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 3. pp. 860-869.
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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.",
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AU - Rochford, Jonathan

AU - Tsai, Ming Kang

AU - Szalda, David J.

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AU - Muckerman, James

AU - Fujita, Etsuko

PY - 2010/2/1

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N2 - 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.

AB - 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.

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