Gradual solid-state redox-isomerism in the lanthanide series.

Oxidation of [(Ar-bian)Yb(dme)] (1) (Ar-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene; dme = 1,2-dimethoxyethane) by 0.5 equivalent of MeNC(S)S-S(S)CNMe in dme at ambient temperature affords a mixture of two products, [(Ar-bian)Yb{SC(S)NMe}(dme)] and [(Ar-bian)Yb{SC(S)NMe}(dme)], which represent two redox-isomers (2a and 2b, respectively). Their ratio in solution depends on the solvent as well as on the temperature.

Digallane with redox-active diimine ligand: dualism of electron-transfer reactions.

The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands.