Thermal Reactions of Systems in Solution 1947-67
Inorganic chemical reactions
Rates of various one-electron exchange reactions between metal ions have been successfully measured, and the long-standing problem of the ferrous-ferric exchange was solved. This has stimulated many investigations in this field of chemical kinetics. It has been found that electron transfer from iron(II) and vanadium(II) proceeds via binuclear complexes in which the donor and acceptor metal ions are connected via a bridging group. Bridging groups vary enormously in their ability to promote electron transfer.
Certain unsymmetrical groups possess two different sites for binding to a metal center. Two complexes containing chromium(III) and thiocyanate have been prepared. In one complex the thiocyanate is attached to the chromium through the nitrogen atom and in the other through the sulfur atom. These two complexes differ considerably in their properties, and they afford one of the very few examples of linkage isomerism. A novel type of intramolecular reorganization reaction, the mercury(II) catalyzed reorganization of a thiocyanate complex, was discovered. In this reaction the metal atom moves from one end of the thiocyanate group to the other. This process may have important implications for mechanisms of more complex reactions.
J. Silverman and R. W. Dodson, "The Exchange Reaction Between the Two
Oxidation States of Iron in Acid Solution," J. Phys. Chem. 56,
Complex organic reactions at low
S. Freed and K. M. Sancier, "Reversible Reaction of Chlorophyll Giving
the Red-Brown Intermediate of the Molisch Phase Test," Science 11,
Last Modified: June 28, 2012