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Carbonyl complexes of chromium, molybdenum and tungsten of the type DAD M(CO) 4  with DAD - diazadiene (R-N=CR′-CR′=NR) are shown by cyclic voltammetry to undergo electron transfer reactions to [DAD M(CO) 4 ] +  and [DAD M(CO)4] - . The rate of subsequent chemical reactions with nucleophiles or by loss of ligands depend on the sol-vent, the metal and the ligands' electronic and steric properties. Chromium(+I) is more readily stabilized than Mo(+I) or W(-I) while the opposite is true for the stability of the anions formed. The dimerisation of a low-coordinate species DAD Mo(CO) 3  from the reduction of DAD Mo(CO) 3 (CH 3 CN) is detected electrochemically. The stabilization of oxidation states +1 and -I is briefly discussed in view of the DAD ligand properties.

zeitschrift für naturforschung b

Zur Elektrochemie von Metall(O)-Verbindungen, V [1] Reaktionen von Diazadien-Metall(VIb)-carbonylkationen und -anionen / Electrochemistry of Metal(O) Compounds, V [1] Reactions of Diazadiene Metal(VIb) Carbonyl Cations and Anions