Reaction of (dioxygen) (dithiocarbamato) rhodium complexes with

Mechanism of Formation of Peroxocarbonates RhOOC(O)O(Cl)(P)3 and Their Reactivity as Oxygen Transfer Agents Mimicking Monooxygenases. The First ...
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Inorg. Chem. 1990, 29, 4204-4208

4204

min. Solutions (and the atmosphere above them) of N O were colorless in the three solvents used. After the introduction of NO, the platinum working electrode was inserted and the cell sealed. The gain on the potentiostat was set to that of the known concentration of NO+BF4-in the particular solvent. At these settings, the concentration of NO was adjusted to give currents nearly the same as that obtained from a 1 X M NO+ solution. Decreasing the concentration of NO was simply performed by allowing argon to flow through the CV cell for a short period of time. This process was repeated until the currents were roughly similar to those of the NO' solutions in a given solvent and at the same scan rate. For the solvents CHJN and N02Me, the voltammograms showed clean diffusive behavior (see Table JI). However, in the cyclic voltammogram of NO in dichloromethane, adsorption at the platinum working electrode was apparent for both the oxidation of N O and the return NO+ reduction waves at concentrations greater than -5 X M. Even at concentrations of