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Comments on Inorganic Chemistry
A Journal of Critical Discussion of the Current Literature
Volume 4, 1985 - Issue 3
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Original Articles

Intramolecular Electron Transfer Reactions of Ion Pairs: Thermal, Optical, and Photochemical Pathways

Pages 113-149 | Published online: 13 Dec 2006

References

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  • Wilkins , R. G. 1974 . The Study of Kinetics and Mechanism of Reactions of Transition Metal Complexes , Boston : Allyn and Bacon . Ligand substitution reactions of transition metal complexes also proceed via similar elementary steps, namely, rapid formation of an outer-sphere adduct between complex and displacing ligand followed by rate-determining ligand interchange. See, for example
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  • This ambiguity represents the microscopic reverse analog of the loss of mechanistic information when the concentrations of reaction products are controlled by thermodynamics rather than by kinetics
  • Alternatively, the kb , pathway may be viewed as proceeding via a different (isomeric) ion pair with a smaller ion-pair formation constant. However, it could conceivably represent a real second-order reaction where, because of the low abundance of pairs of ions having the appropriate metal to ligand bond distances, only a fraction of the collisions results in the transfer of electrons
  • The author is grateful to Dr. N. Sutin and to Professor H. Taube for various suggestions regarding the presence and relative reactivities of isomeric ion pairs
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  • Unfortunately, E0 values for pentaammine cobalt (III) complexes are not available and therefore the calculation is carried out for the ion pair formed between Ru(NH3)5py3+ and Fe(CN)4− 6
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  • This value is in excellent agreement with the value 38 eu calculated from the measured values of Q12 , at 15°C and 25°C (Ref. 6)
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  • Marcus , R. A. and Sutin , N. 1985 . Biochim. Biophys. Acta , in press
  • Since values of E0 , are not available (reductions of the Co(III) complexes are irreversible) and are expected to be small compared to E op, ΔG∗ was taken to be approximately equal to E op/4
  • Powers , M. and Meyer , T. J. 1980 . J. Am. Chem. Soc. , 102 : 1289
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  • It was noted (Ref. 8) that k et for a series of related ligands (carboxylates or pyridines) decreases with increasing pKo , of the protonated ligand. This trend has been ascribed, at least in part, to the increase in the reduction potential of the cobalt(III) complex with decreasing [sgrave]- donor strength of the ligand (Ref. 8)
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  • Battacharjee , S. and Haim , A. to be published
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  • Although E 0 in Eq. (13) is a free energy (Ref. 27), in some instances (Refs. 12 and 22) values of ΔH IP 0 have been utilized instead. Taking ΔH IP 0 as an estimate of E0 (Ref. 12), the calculated values of k et for intramolecular electron transfer in Ru(NH3)5py3+|Fe(CN)4− 6 and Ru(NH3)5py3+|Ru(CN)4− 6 are 4.8 and 2.1 × 10−10 s−1, respectively. There is no improvement in the comparison between calculated (4.8 s−1) and experimental (1.7 × 103 s−1) rate constants for Ru(NH3)5py3+|Fe(CN)6 4, and the necessary difference in rate constants for self-exchange between Fe(CN)3-/4− 6- and Ru(CN)3-/4− 6 reaches the totally unreasonable value of 1012
  • Bolletta , F. , Maestri , M. , Moggi , L. and Balzani , V. 1974 . J. Phys. Chem. , 78 : 1374
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  • Demas , J. N. and Adamson , A. W. 1971 . J. Am. Chem. Soc. , 93 : 1800
  • Juris , A. , Gandolfi , M. T. , Manfrin , M. F. and Balzani , V. 1976 . J. Am. Chem. Soc. , 98 : 1047
  • Kolthoff , I. M. and Tomsicek , W. J. 1935 . J. Phys. Chem. , 39 : 945
  • Kolthoff , I. M. and Tomsicek , W. J. 1936 . J. Phys. Chem. , 40 : 247
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  • Olson , A. R. and Simonson , T. R. 1949 . J. Chem. Phys. , 17 : 1167 The principle of constant ionic strength in kinetics was first questioned by
  • In some instances, notably the Ru(phen)2+ 3-Fe(CN)3− 6 and Ru(bpy)2+ 3-Fe (CN)4− 6- sysstems, the measured values (Ref. 42) displayed a dependence on ionic strength opposite to the assumed dependence
  • Creutz , C. and Sutin , N. 1976 . Inorg. Chem. , 15 : 496
  • Vogler , A. and Kisslinger , J. 1982 . J. Am. Chem. Soc. , 104 : 2311
  • Stritar , J. and Taube , H. 1969 . Inorg. Chem. , 8 : 2281 With this value, the calculated rate constant for the Ru(NH3)5Cl2+−V2− reaction is 1.2 × 103 M−1 s−l, in excellent agreement with the measured value 3.0 × 103 M−1 s−1:, The necessary parameters for the V3+/2+ couple are k, = 3 × 10−3 M−1 s−1 and E 0 = −0.255 v: M. Chou, C. Creutz, and N. Sutin, J. Am. Chem. Soc., 99, 5615 (1977)
  • Newton , M. D. and Sutin , N. 1984 . Ann. Rev. Phys. Chem. , 35 : 437

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