Experimental Evidence for a Temperature Dependent Transition between Normal and Inverse Equilibrium Isotope Effects for Oxidative Addition of H 2 to Ir(PMe2Ph)2(CO)Cl

Journal of the American Chemical Society

Volumn 125, Issue 43, 2003, Pages 13219-13224

  Janak, Kevin E ^a   Parkin, Gerard ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EQUILIBRIUM ISOTOPE EFFECTS (EIE);

ENTROPY; FREQUENCIES; HIGH TEMPERATURE EFFECTS; ISOTOPES; OXIDATION;

HYDROGEN;

CARBON MONOXIDE; CHLORINE DERIVATIVE; HYDROGEN; IRIDIUM;

ADDITION REACTION; ARTICLE; CALCULATION; ENTROPY; ENVIRONMENTAL TEMPERATURE; EQUILIBRIUM CONSTANT; FREQUENCY ANALYSIS; GEOMETRY; HIGH TEMPERATURE PROCEDURES; INVERSE EQUILIBRIUM ISOTOPE EFFECT; LOW TEMPERATURE PROCEDURES; OXIDATION; OXIDATION KINETICS; REFERENCE VALUE; TEMPERATURE MEASUREMENT; VIBRATION;

EID: 0142244912     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0362611     Document Type: Article

References (60)

1. (a) Rabinovich, D.; Parkin, G. J. Am. Chem. Soc. 1993, 115, 353-354.
2. (b) Hascall, T.; Rabinovich, D.; Murphy, V. J.; Beachy, M. D.; Friesner, R. A.; Parkin, G. J. Am. Chem. Soc. 1999, 121, 11 402-11 417.
3. Wolfsberg, M. Acc. Chem. Res. 1972, 5, 225-233.
4. See, for example: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023.
5. (b) Shin, J. H.; Parkin, G. J. Am. Chem. Soc. 2002, 124, 7652-7653.
6. (c) Yan, S. G.; Brunschwig, B. S.; Creutz, C.; Fujita, E.; Sutin, N. J. Am. Chem. Soc. 1998, 120, 10 553-10 554.
7. See, for example: (a) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
8. (b) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120.
9. (c) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214.
10. (d) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825.
11. For some isotope effects in binary metal hydrides, see: (a) Wiswall, R. H., Jr.; Reilly, J. J. Inorg. Chem. 1972, 11, 1691-1696.
12. (b) Luo, W.; Clewley, J. D.; Flanagan, T. B. J. Chem. Phys. 1990, 93, 6710-6722.
13. Bullock, R. M.; Bender, B. R. Isotope Methods in Homogeneous Catalysis. In Encyclopedia of Catalysis; Horváth, I. T., Ed.; 2002.
14. Janak, K. E.; Parkin, G. J. Am. Chem. Soc. 2003, 125, 6889-6891.
15. For other examples of situations in which there is a temperature-dependent transition between a normal and inverse EIE, see ref 2.
16. (a) Deeming, A. J.; Shaw, B. L. J. Chem. Soc. (A) 1969, 1128-1134.
17. (b) Hyde, E. M.; Shaw, B. L. J. Chem. Soc., Dalton Trans. 1975, 765-767.
18. (a) Vaska, L.; Werneke, M. F. Ann. N. Y. Acad. Sci. 1971, 172, 546-562.
19. (b) Zhou, P.; Vitale, A. A.; San Filippo, J., Jr.; Saunders: W. H., Jr. J. Am. Chem. Soc. 1985, 107, 8049-8054.
20. (c) Kunin, A. J.; Johnson, C. E.; Maguire, J. A.; Jones, W. D.; Eisenberg, R. J. Am. Chem. Soc. 1987, 109, 2963-2968.
21. (d) Kunin, A. J.; Farid, R.; Johnson, C. E.; Eisenberg, R. J. Am. Chem. Soc. 1985, 107, 5315-5317.
22. 2 has added parallel to the OC-Ir-X axis, unstable isomers derived from addition parallel to the P-Ir-P axis have also been detected by parahydrogen induced polarization. See: (a) Hasnip, S. K.; Colebrook, S. A.; Sleigh, C. J.; Duckett, S. B.; Taylor, D. R.; Barlow, G. K.; Taylor, M. J. J. Chem. Soc., Dalton Trans. 2002, 743-751.
23. (b) Hasnip, S. K.; Duckett, S. B.; Sleigh, C. J.; Taylor, D. R.; Barlow, G. K.; Taylor, M. J. J. Chem. Soc., Chem. Commun. 1999, 1717-1718.
24. The symmetry factor includes both external (σ) and internal (n) symmetry numbers. See: Bailey, W. F.; Monahan, A. S. J. Chem. Educ. 1978, 55, 489-493.
25. (a) Wolfsberg, M.; Stern, M. J. Pure Appl. Chem. 1964, 8, 225-242.
26. (b) Melander, L.; Saunders: W. H., Jr. Reaction Rates of Isotopic Molecules; Wiley-Interscience: New York 1980.
27. (c) Carpenter, B. K. Determination of Organic Reaction Mechanisms, Wiley-Interscience: New York 1984.
28. (d) Ishida, T. J. Nucl. Sci. Technol. 2002, 39, 407-412.
29. (e) Bigeleisen, J.; Mayer, M. G. J. Chem. Phys. 1947, 15, 261-267.
30. For some recent influential studies concerned with the computation of isotope effects in organometallic systems, see: (a) Slaughter, L. M.; Wolczanski, P. T.; Klinckman, T. R.; Cundari, T. R. J. Am. Chem. Soc. 2000, 122, 7953-7975.
31. (b) Bender, B. R. J. Am. Chem. Soc. 1995, 117, 11 239-11 246.
32. (c) ref 3a and 4a.
33. Application of the Teller-Redlich product rule permits the MMI term to be replaced by the vibrational product (VP) derived from the vibrational frequencies. See ref 13.
34. The EIE at 300 K is 0.57 in good agreement to the value of 0.46 calculated by Krogh-Jespersen and Goldman (ref 3a).
35. rot, the rotational temperature. The EIE data presented here are obtained by treating the rotational and nuclear partition functions classically. Consideration of quantum effects serves to modify the [SYM · MMI · EXC] (entropy) term at low temperature, but has no effect on the low-temperature limit of the EIE which is dominated by the ZPE (enthalpy) term.
36. It should be noted that the ZPE and enthalpy [exp(-ΔΔH/RT)] terms are not identical because the thermal population of vibrationally excited states also provides a contribution to the enthalpy term. Correspondingly, the [SYM · MMI · EXC] and entropy [exp(ΔΔS/R)] terms are not identical, but differ by a similar component to that relating ZPE and enthalpy. However, these differences are small such that ZPE ≈ [exp(-ΔΔH/RT)] and [SYM · MMI · EXC] ≈ [exp(ΔΔS/R)] are good approximations. For example, at 100 K, ZPE = 0.002 and [exp(-ΔΔH/RT)] = 0.002, whereas SYM · MMI · EXC = 5.48, and exp(ΔΔS/R) = 5.48; at 1000 K, ZPE = 0.542 and [exp(-ΔΔH/RT)] = 0.547, whereas SYM · MMI · EXC = 2.12, and exp(ΔΔS/R) = 2.11.
37. EXC is unity at 0 K, and so [SYM · MMI · EXC] = [SYM · MMI]
38. 2)] = 2.04 e.u.
39. 2)] = 1.36 e.u.
40. 2] = Rln(9/4) = 1.61. See: (a) McQuarrie, D. A. "Statistical Mechanics", Harper and Row: New York 1976.
41. (b) Herzberg, G. Molecular Spectra and Molecular Structure. II Infrared and Raman Spectra of Polyatomic Molecules, van Nostrand: New York 1959 pp 508-509.
42. Deeming, A. J.; Shaw, B. L. J. Chem. Soc. (A) 1968, 1887-1889.
43. Torres, L.; Gelabert, R.; Moreno, M.; Iluch, J. M. J. Phys. Chem. A 2000, 104, 7898.
44. Wooley, H. W.; Scott, R. B.; Brickwedde, F. G. J. Res. Natl. Bur. Standards 1948, 41, 379-475.
45. 2 in the absence of contributions from nuclear spin statistics is 3.4 e.u. See ref 18 and Handbook of Chemistry and Physics, 72nd ed.; Lide, D. R., Ed.; CRC Press: Boca Raton 1991; p 5-35.
46. Shin, J. H.; Bridgewater, B. M.; Churchill, D. G.; Parkin, G. Inorg. Chem. 2001, 40, 5626-5635.
47. Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219.
48. toluene = -2047.3/T + 8.330. See: Handbook of Chemistry and Physics, 72nd ed.; Lide, D. R., Ed.; CRC Press: Boca Raton 1991; p 6-84.
49. 2 in benzene: In x = -5.6949-765.47/(T/K). See: Clever, H. L. In Solubility Data Series; Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6: Hydrogen and Deuterium, p 164.
50. 2) has reacted.
51. The van't Hoff plot does not include the high-temperature data due to the deviation from ideal behavior at high temperature (see text).
52. 2 in benzene: In x = -5.7399-743.44/(T/K). See: Clever, H. L. In Solubility Data Series; Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6: Hydrogen and Deuterium, p 287.
53. 2 in toluene: In x = -6.0373-603.07/(T/K). See: Clever, H. L. In Solubility Data Series; Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6: Hydrogen and Deuterium, p 169.
54. 2 in toluene: In x = -6.0781-580.52/(T/K). See: Clever, H. L. In Solubility Data Series; Young, C. L., Ed.; Pergamon Press: Oxford, 1981; Volume 5/6: Hydrogen and Deuterium, p 288.
55. Jaguar 4.1 Schrödinger, Inc., Portland, Oregon, 2001.
56. (a) Slater, J. C. Quantum Theory of Molecules and Solids, Vol. 4: The Self-Consistent Field for Molecules and Solids; McGraw-Hill: New York, 1974.
57. (b) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200-1211.
58. (c) Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
59. (d) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
60. (e) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.