Temperature-dependent transitions between normal and inverse equilibrium isotope effects for coordination and oxidative addition of C-H and H-H bonds to a transition metal center

Journal of the American Chemical Society

Volumn 125, Issue 23, 2003, Pages 6889-6891

  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

TRANSITION ELEMENT;

ADDITION REACTION; ARTICLE; ENERGY; ENTHALPY; ENTROPY; EQUILIBRIUM CONSTANT; HYDROGEN BOND; MOLECULAR INTERACTION; OXIDATION; TEMPERATURE DEPENDENCE; VIBRATION;

EID: 0037601734     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034559l     Document Type: Article

References (30)

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3. For recent reviews, see: (a) Jones, W. D. Acc. Chem. Res. 2003, 36, 140-146.
4. (b) Bullock, R. M.; Bender, B. R. Isotope Methods in Homogeneous Catalysis. In Encyclopedia of Catalysis; Horváth, I. T., Ed.; Wiley-Interscience: Hoboken, NJ, 2002.
5. It should be noted that application of the terms "normal" and "inverse" to describe an EIE requires consideration of the direction of the reaction. Thus, if the EIE for oxidative addition were to be inverse, that for reductive elimination would be normal.
6. See, for example: (a) Hascall, T.; Rabinovich, D.; Murphy, V. J.; Beachy, M. D.; Friesner, R. A.; Parkin, G. J. Am. Chem. Soc. 1999, 121, 11402-11417.
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10. d (a) Wick, D. D.; Reynolds, K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974-3983. (b) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (c) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897-3908. (d) Churchill, D. G.; Janak, K. E.; Wittenberg, J. S.; Parkin, G. J. Am. Chem. Soc. 2003, 125, 1403-1420.
11. d (a) Wick, D. D.; Reynolds, K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974-3983. (b) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (c) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897-3908. (d) Churchill, D. G.; Janak, K. E.; Wittenberg, J. S.; Parkin, G. J. Am. Chem. Soc. 2003, 125, 1403-1420.
12. d (a) Wick, D. D.; Reynolds, K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974-3983. (b) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (c) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897-3908. (d) Churchill, D. G.; Janak, K. E.; Wittenberg, J. S.; Parkin, G. J. Am. Chem. Soc. 2003, 125, 1403-1420.
13. d (a) Wick, D. D.; Reynolds, K. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 3974-3983. (b) Wang, C.; Ziller, J. W.; Flood, T. C. J. Am. Chem. Soc. 1995, 117, 1647-1648. (c) Bullock, R. M.; Headford, C. E. L.; Hennessy, K. M.; Kegley, S. E.; Norton, J. R. J. Am. Chem. Soc. 1989, 111, 3897-3908. (d) Churchill, D. G.; Janak, K. E.; Wittenberg, J. S.; Parkin, G. J. Am. Chem. Soc. 2003, 125, 1403-1420.
14. 2(CO)H. See ref 4c.
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19. All calculations were carried out using DFT as implemented in the Jaguar 4.1 suite of ab initio quantum chemistry programs.
20. (a) Wolfsberg, M.; Stern, M. J. Pure Appl. Chem. 1964, 8, 225-242.
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22. (c) Carpenter, B. K. Determination of Organic Reaction Mechanisms; Wiley-Interscience: New York, 1984.
23. Janak, K. E.; Churchill, D. G.; Parkin, G. Chem. Commun. 2003, 22-23.
24. Bender, B. R., unpublished results cited in ref 2b.
25. In terms of ΔH and ΔS, a simple exponential variation of K as a function of temperature, according to K = exp(-ΔH/RT)exp(ΔS/R), merely requires that ΔH and ΔS do not vary significantly over the temperature range studied. The existence of a maximum and a transition between normal and inverse EIEs is a result of ΔS being temperature dependent.
26. rot, the rotational temperature. However, this variation has no effect on the actual low-temperature limit of the EIE.
27. The ZPE term increases from zero to a limiting value of unity as the temperature is increased, while EXC decreases from unity to a limiting value of I/MMI (i.e., I/VP).
28. 2]W}, the MMI/VP ratios are 1.05 and 1.01, respectively. These discrepancies have little effect on the derived EIE.
29. See ref 2b for a description of the six new vibrations. Note that, although there are six new vibrations, they do not contribute equally to the EIE.
30. 2 for which both normal and inverse EIEs have been discussed, see: Kotaka, M.; Okamoto, M.; Bigeleisen, J. J. Am. Chem. Soc. 1992, 114, 6436-6445.