References
- Sutin , N. 1968 . Ace. Chem. Res. , 1 : 225
- 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
- Haim , A. 1983 . Pure Appl. Chem. , 55 : 89
- Haim , A. 1983 . Prog. Inorg. Chem. , 30 : 273
- Gaswick , D. G. and Haim , A. 1971 . J. Am. Chem. Soc. , 93 : 7347
- Miralles , A. J. , Armstrong , R. E. and Haim , A. 1977 . J. Am. Chem. Soc. , 99 : 1416
- Miralles , A. J. , Szecsy , A. P. and Haim , A. 1982 . Inorg. Chem. , 21 : 697
- Kremer , E. , Cha , G. , Morkevicius , M. , Seaman , M. and Haim , A. 1984 . Inorg. Chem. , 23 : 3028
- Oliveira , L. A. A. , Giesbrecht , E. and Toma , H. E. 1979 . J. Chem. Soc. Dallon , : 236
- 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
- Sutin , N. 1983 . Prog. Inorg. Chem. , 30 : 441
- Curtis , J. C. and Meyer , T. J. 1982 . Inorg. Chem. , 21 : 1562
- Brown , G. M. and Sutin , N. 1979 . J. Am. Chem. Soc. , 101 : 883
- Szecsy , A. P. and Haim , A. 1981 . J. Am. Chem. Soc. , 103 : 1679
- Casabó , J. and Ribas , J. 1977 . Inorg. Chim. Acta , 21 : 5
- 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
- Yee , E. L. and Weaver , M. J. 1980 . Inorg. Chem. , 19 : 1077
- Hupp , J. T. and Weaver , M. J. 1984 . Inorg. Chem. , 23 : 256
- 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)
- Ahrland , S. 1972 . Coord. Chem. Rev. , 8 : 21
- Bertram , H. and Wieghardt , K. 1979 . Inorg Chem. , 18 : 1799
- Nakahara , A. and Wang , J. H. 1963 . J. Phys. Chem. , 67 : 496
- Curtis , J. C. , Sullivan , B. P. and Meyer , T. J. 1980 . Inorg. Chem. , 19 : 3833
- Oliveira , L. A. A. and Haim , A. 1981 . J. Am. Chem. Soc. , 104 : 3363
- Hush , N. S. 1967 . Prog. Inorg. Chem. , 8 : 391
- Creutz , C. 1983 . Prog. Inorg. Chem. , 30 : 1
- Sutin , N. 1981 . Ace. Chem. Res. , 15 : 275
- 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
- Sutin , N. and Creutz , C. Inorganic Reactions and Methods , Edited by: Zuckerman , J. J. Berlin : Springer-Verlag . in press
- Sutin , N. and Brunschwig , B. S. 1982 . ACS Symp. Ser. , 198 : 105
- Sutin , N. 1973 . Inorg. Biochem. , 2 : 611
- 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)
- Fan , F.-R. F. and Gould , E. S. 1974 . J. Am. Chem. Soc. , 13 : 2647
- Haim , A. and Sutin , N. 1976 . Inorg. Chem. , 15 : 476
- Meyer , T. J. and Taube , H. 1968 . Inorg. Chem. , 7 : 2369
- Toma , H. E. 1980 . J. Chem. Soc. Dalton , : 471
- Vogler , A. and Kisslinger , J. 1982 . Angew. Chem. Int. Ed. Eng. , 21 : 77
- Battacharjee , S. and Haim , A. to be published
- Sabbatini , N. , Bonazzi , A. , Ciano , M. and Balzani , V. 1984 . J. Am. Chem. Soc. , 106 : 4055
- Juris , A. , Manfrin , M. F. , Maestri , M. and Serpone , N. 1978 . Inorg. Chem. , 17 : 2258
- Rybak , W. , Haim , A. , Netzel , T. L. and Sutin , N. 1981 . J. Phys. Chem. , 85 : 2856
- Demas , J. N. and Addington , J. W. 1976 . J. Am. Chem. Soc. , 98 : 5800
- Holtzwarth , J. and Jurgensen , H. 1974 . Ber. Bunsenges. Phys. Chem. , 78 : 526
- Brunschwig , B. and Sutin , N. 1978 . J. Am. Chem. Soc. , 100 : 7568
- Creutz , C. , Chou , M. , Netzel , T. L. , Okumura , M. and Sutin , N. 1980 . J. Am. Chem. Soc. , 102 : 1309
- 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
- Kalyanasundaram , K. 1982 . Coord. Chem. Rev. , 46 : 159
- 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
- Campion , R. J. , Deck , C. F. , King , P. Jr. and Wahl , A. C. 1967 . Inorg. Chem. , 6 : 672
- 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