Guide Electrochemistry in Nonaqueous Solutions, 2nd Edition

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Kolthoff at the University of Minnesota from to His research interest lies in electroanalytical chemistry in nonaqueous solutions and he has published over original papers and many review articles on the subject. Free Access. Tools Get online access For authors.

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Steckhan, Ed. Yeager, J. Bockris, B. Yeager, A. Salkind, Eds. Roller, R. Fundamentals Ch McNaught, A. Bard, L. References 29 Ch A practical consideration in selecting these materials is that the materials should be easily process- able, inert to the electrochemical reactions, and cost-effective.

Supposedly, this was caused by the formation of the base-off CN 2 Co III form with an electron rich cobalt centre which is more difficult to reduce.

A similar observation has already been described for cyanocobalamin 1. Ag—AgCl, a mixture quantitatively transformed into a final Co I form. Ag—AgCl Fig. No formation of dicyanocobalester was observed in 2 Fig. To further confirm the existence of CN Co II intermediate 5 and a key role of axial ligand exchange in the generation of Co I species 7 , the reaction environment was modified in the following manner Fig.

Firstly, the cyclic voltammogram was recorded using THF as a solvent.

In contrast to the experiment in MeCN, a second reduction peak appeared at ca. Ag—AgCl, indicating the direct reduction of cyano-form 5 to Co I complex 7. Such a behavior is consistent with our mechanistic hypothesis, as weaker coordination abilities compared to MeCN towards transition metals result in a lower K II Cble value and afford stabilization of CN Co II complex 5 under the experimental conditions Scheme 2.

References

Due to changes at the periphery of the corrin ring, we expected cyanide ligand exchange to be altered. The use of carbon felt as a working electrode proved superior over Pt, which was consistent with the conditions of cyclic voltammetry measurements compare entries 1 and 2. As expected, the use of THF as a solvent entry 3 led to a dramatic decrease in the yield, due to impeded generation of active Co I species 7.


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Lowering the concentration of the starting material only slightly affected the yield entry 4. Ag—AgCl still allowed for an efficient reaction to occur entry 5 , however, no further decrease was possible data not shown.