Electron exchange involving a sulfur-stabilized ruthenium radical cation

Anthony P. Shaw, Bradford L. Ryland, Jack R. Norton, Daniela Buccella, Alberto Moscatelli

Research output: Contribution to journalArticle

Abstract

Half-sandwich Ru(II) amine, thiol, and thiolate complexes were prepared and characterized by X-ray crystallography. The thiol and amine complexes react slowly with acetonitrile to give free thiol or amine and the acetonitrile complex. With the thiol complex, the reaction is dissociative. The thiolate complex has been oxidized to its Ru(III) radical cation and the solution EPR spectrum of that radical cation recorded. Cobaltocene reduces the thiol complex to the thiolate complex. The 1H and 31P NMR signals of the thiolate complex in acetonitrile become very broad whenever the thiolate and thiol complexes are present simultaneously. The line broadening is primarily due to electron exchange between the thiolate complex and its radical cation; the latter is generated by an unfavorable redox equilibrium between the thiol and thiolate complexes. Pyramidal inversion of sulfur in the thiol complex is fast at room temperature but slow at lower temperatures; major and minor conformers of the thiol complex were observed by 31P NMR at -98°C in CD 2Cl2.

Original languageEnglish (US)
Pages (from-to)5805-5812
Number of pages8
JournalInorganic Chemistry
Volume46
Issue number14
DOIs
StatePublished - Jul 9 2007

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Ruthenium
Sulfur
Sulfhydryl Compounds
thiols
ruthenium
Cations
sulfur
cations
Electrons
electrons
acetonitrile
Amines
amines
Nuclear magnetic resonance
nuclear magnetic resonance
X ray crystallography
crystallography
Paramagnetic resonance
inversions
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Electron exchange involving a sulfur-stabilized ruthenium radical cation. / Shaw, Anthony P.; Ryland, Bradford L.; Norton, Jack R.; Buccella, Daniela; Moscatelli, Alberto.

In: Inorganic Chemistry, Vol. 46, No. 14, 09.07.2007, p. 5805-5812.

Research output: Contribution to journalArticle

Shaw, AP, Ryland, BL, Norton, JR, Buccella, D & Moscatelli, A 2007, 'Electron exchange involving a sulfur-stabilized ruthenium radical cation', Inorganic Chemistry, vol. 46, no. 14, pp. 5805-5812. https://doi.org/10.1021/ic700580u
Shaw, Anthony P. ; Ryland, Bradford L. ; Norton, Jack R. ; Buccella, Daniela ; Moscatelli, Alberto. / Electron exchange involving a sulfur-stabilized ruthenium radical cation. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 14. pp. 5805-5812.
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