Abstract
(Bpz)M(CN)42- (M = Fe, Ru) and (abpy)Fe(CN)42- with the strongly p-accepting chelate ligands 2,2'-bipyrazine (bpz) and 2,2'-azobis(pyridine) (abpy) were prepd. as potassium or tetrabutylammonium salts and were characterized by IR and UV/visible absorption spectroscopy. Cyclic voltammetry in acetonitrile, DMF, or water revealed reversible 1-electron oxidn. processes, while the redn. waves showed reversibility only in aprotic solvents. EPR studies of the spectroelectrochem. generated (1-) and (3-) states confirm the MLCT formulation for the lowest excited states of the (2-) precursor complexes by showing typical low-spin Fe(III) signals of the oxidized species (abpy)Fe(CN)4- and partially hyperfine-structured spectra for the reduced forms (bpz)M(CN)43-. The latter are clearly tetracyanoiron(II) or -ruthenium(II) complexes of the corresponding anion radical acceptor ligands and are thus isoelectronic with monoanionic tetracarbonylchromium(0) or -molybdenum(0) radial complexes. on SciFinder(R)
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