By Henry Taube
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Extra info for Electron Transfer Reactions of Complex Ions in Solution
R. E. Connick, private communication. 15. T h e notation Ce(IV) rather than Ce 4 f is chosen because the ion hydrolyzes quite strongly in acid, and the constitution of the ion is sensitive to acidity. 16. O. Schmitz-Dumont, H. Brokopf, and K. Burkhardt, Z. Anorg. Allgem. Chem. 295, 7 (1958). 17. H. Baldwin and H. Taube, / . Chem. Phys. 33, 206 (1960). 18. R. E. Connick and D. N . Fiat, J. Chem. Phys. 39, 1349 (1963). 19. R. E. Connick and D . N. Fiat, / . Chem. Phys. 44, 4103 (1966). 20. J. A. Jackson, J.
Proof of this kind of mechanism may be difficult to obtain unless the intermediate seven-coordinate V(III) has a fairly long lifetime. In contrast to the case discussed, when a one-electron oxidant attacks a reducing agent in which the t2g orbitals are occupied by electron pairs, an antibonding electron is still left in the same orbital after the reducing agent transfers one to the oxidant, so that the ligand given up by the oxidant cam ^t penetrate the first coordination sphere of the reducing agent.
ACTIVATED COMPLEXES FOR ELECTRON TRANSFER by an inner-sphere mechanism depended on choosing a system in which the opportunity mentioned could easily be exploited. The reaction studied was the reduction of Co(NH 3 ) 5 Cl 2+ by Cr 2+ . The system was chosen with the knowledge that the Co(III) complex retains its integrity in solution for a long period of time, that Cr2+ is labile to substitution, that Co2+ is labile to substitu tion, that CrCl 2 + is slow to aquate, and with the hope that Cr 2 + would reduce Co(III) rapidly.