Reduction of the dinuclear Co(II) nindigo complex dmp(2)Nin[Co(N{SiMe(3)}(2))](2), with 1 or 2 equiv. of K(0) (or KC(8)), affords the reduced complexes [dmp(2)Nin{Co(N{SiMe(3)}(2))}(2)](-) and [dmp(2)Nin{Co(N{SiMe(3)}(2))}(2)](2-), respectively. Inspection of these reduced species reveals ligand-centered reduction, with each cobalt ion retaining a formal 2+ oxidation state.
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A dinuclear cobalt complex featuring unprecedented anodic and cathodic redox switches for single-molecule magnet activity.
J Am Chem Soc
October 2013
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
One-electron oxidation or reduction of the paramagnetic dinuclear Co(II) complex dmp2Nin{Co[N(SiMe3)2]}2 (1; dmp2Nin(2-) = bis(2,6-dimethylphenyl)nindigo), by fully reversible chemical or electrochemical methods, generates the radical salts [1(OEt2)](+) and [1](-), respectively. Full structural and magnetic analyses reveal the locus of the redox changes to be nindigo-based, thus giving rise to ligand-centered radicals sandwiched between two paramagnetic and low-coordinate Co(II) centers. The presence of these sandwiched radicals mediates magnetic coupling between the high-spin (S = 3/2) cobalt ions, which gives rise to single-molecule magnet (SMM) activity in both the oxidized ([1(OEt2)](+)) and reduced ([1](-)) states.
View Article and Find Full Text PDFProbing the redox non-innocence of dinuclear, three-coordinate Co(II) nindigo complexes: not simply β-diketiminate variants.
Chem Commun (Camb)
November 2012
Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, Indiana, USA.
Reduction of the dinuclear Co(II) nindigo complex dmp(2)Nin[Co(N{SiMe(3)}(2))](2), with 1 or 2 equiv. of K(0) (or KC(8)), affords the reduced complexes [dmp(2)Nin{Co(N{SiMe(3)}(2))}(2)](-) and [dmp(2)Nin{Co(N{SiMe(3)}(2))}(2)](2-), respectively. Inspection of these reduced species reveals ligand-centered reduction, with each cobalt ion retaining a formal 2+ oxidation state.
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