Reaction progress kinetic analysis: A powerful methodology for mechanistic studies of complex catalytic reactions

Angewandte Chemie - International Edition

Volumn 44, Issue 28, 2005, Pages 4302-4320

  Blackmond, Donna G ^a  

^a IMPERIAL COLLEGE LONDON   (United Kingdom)

Author keywords

Catalysis; In situ measurements; Kinetics; Reaction kinetics; Reaction mechanisms

Indexed keywords

KINETIC ANALYSIS; MECHANISTIC MODELS; RATE EQUATIONS; REACTION PROGRESS;

GRAPHIC METHODS; MATHEMATICAL MODELS; REACTION KINETICS;

CATALYSIS;

CHALCONE DERIVATIVE; ENZYME; ORGANOMETALLIC COMPOUND;

CATALYSIS; CHEMICAL MODEL; CHEMISTRY; KINETICS; REVIEW;

CATALYSIS; CHALCONES; ENZYMES; KINETICS; MODELS, CHEMICAL; ORGANOMETALLIC COMPOUNDS;

EID: 22744443220     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200462544     Document Type: Review

References (48)

1. H. Lineweaver, D. Burk, J. Am. Chem. Soc. 1934, 56, 658.
2. Chem. Eng. News 2003, 81, 25.
3. L. Michaelis, M. Menten, Biochem. Z. 1913, 49, 1333.
4. The Michaelis Menten rate law was conceived first by Victor Henri (V. Henri, C. R. Hebd. Seances Acad. Sci. 1902, 135, 916).
5. [1] (C. S. Hanes, Biochem. J. 1932, 26, 1406).
6. The Lineweaver-Burk and other related graphical methods are covered in detail in enzyme kinetics textbooks. For an especially lucid discussion of both the history and the use of graphical methods in general and the opportunities and limitations of such methods, see A. Cornish-Bowden, Enzyme Kinetics, 3rd ed., Portland, London, 2004.
7. Extensive graphical methods have been developed, primarily for studying enzyme kinetics, for consideration of reaction complexities such as product inhibition by using a classical kinetic approach, which entailed a concomitant increase in the number of required experiments. The textbook cited in Ref. [4] provides an excellent background to these methods.
8. Rate may be calculated from (concentration, time) data sets by fitting the data to an arbitrary function (e.g., a 9th order polynomial) and then differentiating this function to obtain (rate, time) data. Care must be taken to insure that the fit is accurate to obtain an accurate rate profile.
9. M. Ropic, D. G. Blackmond, unpublished results.
10. T. Rosner, M. Baumann, A. Togni, D. G. Blackmond, unpublished results.
11. S. Eyley, personal communication.
12. J. LeBars, D. G. Blackmond, unpublished results.
13. J. S. Mathew, D. G. Blackmond, unpublished results.
14. A. Soheili, J. Albaneze-Walker, J. A. Murry, P. G. Dormer, D. L. Hughes, Org. Lett. 2003, 5, 4191.
15. The use of a corroborating technique also helps check the validity of the method when the question of complications other than side reactions arises. For example, the extent of contribution to the overall signal from physical processes such as heat of mixing or heat of precipitation may be quantified by using reaction calorimetry, while by using FTIR spectroscopy the possibility of an inhomogeneous solution layer adjacent to the IR window may be explored.
16. For a review, see: M. Studer, H.-U. Blaser, Adv. Synth. Catal. 2003, 345, 45.
17. F. Bohnen, A. Gomez, D. G. Blackmond, unpublished results.
18. -1.
19. F. G. Helfferich, Kinetics of Homogeneous Multi-Step Reactions, Elsevier, Amsterdam, 2001, chap 7.2.
20. The concentration of 2 is strictly given by: [2] = ["excess"] + [1] + [5]; however, [5] may be neglected under typical catalytic conditions where [5] ≪ [1] and [5] ≪ ["excess"]. This consideration helps to set a lower limit on ["excess"]. In general, practical values of ["excess"] should be at least an order of magnitude greater than the catalyst concentration.
21. a) S. Colonna, H. Molinari, S. Banfi, S. Juliá, J. Masana, A. Alvarez, Tetrahedron 1983, 39, 1635;
22. b) S. Banfi, S. Colonna, H. Molinari, S. Juliá, J. Guixer, Tetrahedron 1984, 40, 5207, and references therein;
23. c) R. W. Flood, T. P. Geller, S. A. Petty, S. M. Roberts, J. Skidmore, M. Volk, Org. Lett. 2001, 3, 683.
24. S. P. Mathew, S. Gunathilagan, D. G. Blackmond, unpublished results.
25. The graphical tools described here may only be used where the steady-state approximation applies. For many catalytic reactions this rules out data at the very start of the reaction if an induction period is present (see Section 7.1.1). By definition, the steady-state approximation breaks down for the last few turnovers of the reaction, where the concentration of the catalytic intermediate species approaches that of the substrates being consumed and the parameter ["excess"] is no longer constant (see discussion in Ref. [18]). These graphical tools are generally recommended for use on reaction progress data between 15 and 85 % conversion of the limiting substrate.
26. Figure 8a was redrawn in a different form from T. Rosner, J. LeBars, A. Pfaltz, D. G. Blackmond, J. Am. Chem. Soc. 2001, 123, 1848.
27. J. LeBars, C. P. Stevenson, E. N. Jacobsen, D. G. Blackmond, unpublished results.
28. Reviews: R. F. Heck, Org. React. 1982, 27, 345-390;
29. A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473-2506;
30. Angew. Chem. Int. Ed. Engl. 1994, 33, 2379-2411;
31. W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2-7.
32. a) M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacobsen, Science 1997, 277, 936;
33. b) J. M. Keith, J. F. Larrow, E. N. Jacobsen, Adv. Synth. Catal. 2001, 343, 109.
34. For a detailed kinetic analysis of this reaction, see L. P. C. N. Nielsen, C. P. Stevenson, D. G. Blackmond, E. N. Jacobsen, J. Am. Chem. Soc. 2004, 126, 1360.
35. Figure 9a was constructed from the data in: T. Rosner, J. LeBars, A. Pfaltz, D. G. Blackmond, J. Am. Chem. Soc. 2001, 123, 1848.
36. A. F. Littke, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 6989.
37. C. Ellis, D. G. Blackmond, unpublished results.
38. The high ee value achieved in this reaction justifies the simplification of the treatment to include only one catalytic cycle.
39. a) A. H. M. deVries, J. F. G. A. Jansen, B. L. Feringa, Tetrahedron 1994, 50, 4479;
40. b) C. Bolm, M. Ewald, M. Felder, Chem. Ber. 1992, 125, 1205.
41. H. Iwamura, F. G. Buono, D. G. Blackmond, unpublished results.
42. H. Iwamura, F. G. Buono, D. G. Blackmond, unpublished results.
43. The data were fit using the Solver program in Excel. Statistical analysis was performed using Solvstat.xls, a macro program for use with Excel that is available with E. J. Billo, Excel for Chemists, Wiley-VCH, New York, 2001.
44. -1. While the units of molarity cancel these are, in reality, molarities of two different substances. The right hand side of Equation (16) shows clearly that TOF exhibits a concentration dependence.
45. For a lucid discussion of the concept of the rate-limiting step, see K. J. Laidler, J. Chem. Educ. 1988, 65, 250.
46. For examples of kinetic modeling studies of reactions exhibiting more complex mechanisms, see: a) T. Rosner, P. J. Sears, W. A. Nugent, D. G. Blackmond, Org. Lett. 2000, 2, 2511;
47. b) D. G. Blackmond, C. R. McMillan, S. Ramdeehul, A. Schorm, J. M. Brown, J. Am. Chem. Soc. 2001, 123, 10103;
48. c) F. G. Buono, P. J. Walsh, D. G. Blackmond, J. Am. Chem. Soc. 2002, 124, 13652; also see Ref. [26].