Accessing the different redox states of α-lminopyridines within cobalt complexes

Connie C. Lu, Thomas Weyhermuller, Eckhard Bill, Karl Wieghardt

Research output: Contribution to journalArticle

62 Scopus citations

Abstract

Cobalt coordination complexes featuring the redox-active α-iminopyridine ligand are described. The quite reducing bis-(ligand)cobalt monoanion (1red) was isolated and characterized by X-ray crystallography. The complex forms a three-membered electron-transfer series along with its neutral and monocationic counterparts, which were previously reported. The electronic structures in this series are all consistent with divalent cobalt and the redox events being ligand-centered. The reactivity profile of 1red was briefly explored, and two new compounds were isolated, bis(ligand)-methylcobalt (2) and bis(ligand)iodocobalt (3). Though 2 and 3 are isostructural, they are characterized by different electronic structures. The methylcobalt complex is best described by a Co(111) center with two ligand radicals, whereas the iodocobalt species is more aptly assigned as a Co(11) center with only one ligand radical. Further evidence of their different electronic structures is that a low-lying excited state is populated at room temperature in the case of the iodocobalt compound, whereas the methylcobalt complex is an energetically well-isolated spin singlet. Magnetic susceptibility data, structural data, variable temperature NMR spectroscopy, and density functional theory calculations lend support to this proposal.

Original languageEnglish (US)
Pages (from-to)6055-6064
Number of pages10
JournalInorganic Chemistry
Volume48
Issue number13
DOIs
StatePublished - Jul 6 2009

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