Abstract
Complex cations Ni(C5R5)(L)+, L = 1,4-diphenyl-2,3-dimethyl-1,4-diaza-1,3-butadiene, were compared as structurally characterized BF4- (R = H) and SbF6- salts (R = Me). These NiII(L0) compds. are reversibly reduced (R = H,Me) or oxidized (R = Me) and their one-electron oxidized and reduced forms studied by EPR and UV/Vis spectroelectrochem., supported by DFT calcns. Surprisingly similar EPR features were obsd. for Ni(C5Me5)(L)0 and Ni(C5Me5)(L)2+. Whereas the oxidn. is largely metal centered to yield a NiIII species (R = Me), the redn. reveals energetically close-lying alternatives (redox isomers) NiI(L0) and NiII(L·-). on SciFinder(R)
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