Add time:08/25/2019         Source:sciencedirect.com

The synthesis and electrochemical behaviour of the nickel(II) macrocyclic derivatives [Ni(MC1)L](ClO4) and [Ni(MC2)L](ClO4) where MC1 is 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and MC2 is 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene, and L− stands for the 1,1-dithio monoanions, dimethyldithiocarbamate (Me2Dtc−), diethyldithiocarbamate (Et2Dtc−) or pyrrolidindithiocarbamate (PyDtc−), are described. The analytical and spectroscopic data are consistent with a pentacoordinate geometry. Electrochemical studies of these complexes indicate a reversible oxidation process yielding nickel(III) species unstable at room temperature. EPR studies indicate that these short-lived low-spin d7 nickel(III) species have their unpaired electron in the dz2 orbital.

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