1973 Volume 46 Issue 10 Pages 3095-3098
The mechanism of the reductive cleavage of organic halides (RX) by pentacyanocobaltate(II) Co(CN)53− was investigated by means of the extended Hückel MO theory. First, the molecular structure of Co(CN)53− was considered to be the square-pyramidal C4V configuration, without H2O as its sixth ligand. Secondly, the order of the observed rate constants for the Co(CN)53−+RX→Co(CN)5X3−+R. reaction was found to be in satisfactory accordance with that of the calculated binding energies of the R-X bond. Thirdly, the reductive cleavage of RX by Co(CN)53− proceeds by the aid of the predominant electron-migration from the highest-occupied, lone-pair halogen-orbital to the singly-occupied dz2 Co-orbital and from the highest-occupied dxz (or dyz) Co-orbital to the lowest-unoccupied, antibonding pσ* orbital of the R–X bond. Finally, the mode of the interaction between Co(CN)53− and RX was precisely discussed in terms of the homolytic cleavage of the R–X bond.
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