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The Walden inversion in the reactions of cobalt complexes

J. C. Bailar

The University of Illinois, Urbana, Illinois, U.S.A.


Abstract: The exptl. work on the Walden inversion in the reactions of Co complexes for the last 3 decades was described. It was detd. that in the Walden reaction between NH3 and [Co(en)2Cl2]Cl, the diammine complex is formed showing dextro rotation at one wavelength and levo rotation at another. If the dispersion curve crosses the zero line very close to the Na-D line, then the substance although optically active at that wavelength shows zero rotation. It was detd. that the key to the whole inversion reaction is the removal of a proton from the complex. This leaves a neg. charge on that N atom and allows it to move toward an adjacent coordinated Cl atom. A OH- from the soln. takes the place which the N originally occupied, and the Cl atom is released from the complex. This release is facilitated by the presence of Ag ion, but is effected in the absence of Ag ion if the concn. of OH- is sufficiently large. The amine N eventually combines with a proton from the solvent to become, again part of an NH2 group.

Full paper in Portable Document Format: 193a153.pdf


Chemical Papers 19 (3) 153–160 (1965)

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