Two-state reactivity as a new concept in organometallic chemistry

Accounts of Chemical Research

Volumn 33, Issue 3, 2000, Pages 139-145

  Schröder, Detlef ^a   Shaik, Sason ^b   Schwarz, Helmut ^a  

^a TECHNISCHE UNIVERSITÄT BERLIN   (Germany)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOMETALLIC COMPOUND; RADICAL;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMISTRY; MATHEMATICAL ANALYSIS; REACTION ANALYSIS;

ORGANOMETALLIC COMPOUNDS;

EID: 0037742151     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar990028j     Document Type: Article

References (52)

1. For an advanced view, see: Robb, M. A.; Bernardi, F.; Olivucci, M. Conical intersections as a mechanistic feature in organic photochemistry. Pure Appl. Chem. 1995, 67, 783.
2. Shaik, S.; Danovich, D.; Fiedler, A.; Schröder, D.; Schwarz, H. Two-State Reactivity in Organometallic Gas-Phase Ion Chemistry. Helv. Chim. Acta 1995, 78, 1393.
3. In a more strict sense, the lowest-lying route involving both spin surfaces is the adiabatic reaction coordinate, while the spin-conserving route following the initial spin states of the reactants corresponds to the diabatic variant.
4. 2- with Hydrocarbons. Acc. Chem. Res. 1993, 26, 213.
5. Shaik, S.; Filatov, M.; Schröder, D.; Schwarz, H. Electronic Structure Makes a Difference: Cytochrome P-450 Mediated Hydroxylations of Hydrocarbons as a Two-State Reactivity Paradigm. Chem. Eur. J. 1998, 4, 193.
6. Armentrout, P. B. Chemistry of Excited Electronic States. Science 1991, 251, 175.
7. 2? J. Am. Chem. Soc. 1986, 108, 2765.
8. 8 Total Cross Section at 0.22 eV. J. Phys. Chem. 1990, 94, 5655.
9. 6S) and Thermochemistry of Neutral and Ionic Chromium-Carbon Bonds. J. Am. Chem. Soc. 1992, 114, 2039.
10. + with Propane, Butane, Methylpropane, and Dimethylpropane. J. Am. Chem. Soc. 1992, 114, 2050.
11. 8. J. Am. Chem. Soc. 1992, 114, 1083.
12. + with Water. J. Am. Chem. Soc. 1999, 121, 574 and references therein.
13. + in the Gas Phase: Structure, Electronic States, and the Reactivity with Hydrogen and Hydrocarbons. J. Am. Chem. Soc. 1996, 118, 9941.
14. + (M = Ti, V, Zr, Nb) in the gas phase. Int. J. Mass Spectrom. 1999, 182/183, 85.
15. +: Excited-State Effects on the Mechanism for C-H Bond Activation from Kinetic Energy Release Distributions. J. Am. Chem. Soc. 1997, 119, 3935.
16. 4. J. Chem. Phys. 1997, 106, 1421.
17. (a) Detrich, J. L.; Reinaud, O. M.; Rheingold, A. L.; Theopold, K. H. Can Spin State Change Slow Organometallic Reactions? J. Am. Chem. Soc. 1995, 117, 11745.
18. 2. J. Am. Chem. Soc. 1997, 119, 2516.
19. (a) Rappé, A. K.; Upton T. H. Activation of dihydrogen by scandium ions. J. Chem. Phys. 1986, 85, 4400.
20. 4F) and Propane. J. Phys. Chem. 1987, 97, 4433.
21. For an approximate treatment of spin crossover in the association of atomic Ni with CO, see: Mitchell, S. A. Association Reactions of Transition Metal Atoms with simple Molecules near Room Temperature. In Gas-Phase Metal Reactions; Fontijn, A., Ed.; Elsevier: Amsterdam, 1992; p 227.
22. + and Water. J. Phys. Chem. 1994, 98, 68.
23. 2. J. Phys. Chem. 1994, 98, 6522.
24. + in the gas phase as studied by multiple mass spectrometric techniques. Int. J. Mass Spectrom. Ion Processes 1997, 161, 175.
25. (a) Fiedler, A.; Schröder, D.; Shaik, S.; Schwarz, H. Electronic Structures and Gas-Phase Reactivities of Cationic Late-Transition-Metal Oxides. J. Am. Chem. Soc. 1994, 116, 10734.
26. +. Selection Rules and Reactivity Effects. J. Am. Chem. Soc. 1997, 119, 1773.
27. +: Addition-Elimination, "Rebound", and Oxene-Insertion Mechanisms. J. Phys. Chem. A 1998, 102, 3835.
28. + with Water. J. Am. Chem. Soc. 1999, 121, 8549.
29. Schröder, D.; Schwarz, H. C-H- und C-C-Bindungsaktivierung durch "nackte" Übergangsmetalloxid-Kationen in der Gasphase. Angew. Chem. 1995, 107, 2126; C-H and C-C Bond Activation by Bare Transition-Metal Oxide Cations in the Gas Phase. Angew. Chem., Int. Ed. Engl. 1995, 34, 1973.
30. Schröder, D.; Schwarz, H. C-H- und C-C-Bindungsaktivierung durch "nackte" Übergangsmetalloxid-Kationen in der Gasphase. Angew. Chem. 1995, 107, 2126; C-H and C-C Bond Activation by Bare Transition-Metal Oxide Cations in the Gas Phase. Angew. Chem., Int. Ed. Engl. 1995, 34, 1973.
31. Filatov, M.; Harris, N.; Shaik, S. A theoretical study of electronic factors affecting hydroxylation by model ferryl complexes of cytochrome P-450 and horseradish peroxidase. J. Chem. Soc., Perkin Trans. 2 1999, 399.
32. SI may be incorporated in the preexponential factor of an Arrhenius formalism.
33. +). J. Phys. Chem. A 1998, 102, 5305 and references therein.
34. Plattner, D. A. Spinumkehr und Reaktivität. Angew. Chem. 1999, 111, 86; Interspin Crossing and Reactivity. Angew. Chem., Int. Ed. 1999, 38, 82.
35. Plattner, D. A. Spinumkehr und Reaktivität. Angew. Chem. 1999, 111, 86; Interspin Crossing and Reactivity. Angew. Chem., Int. Ed. 1999, 38, 82.
36. (a) Kretzschmar, I.; Schröder, D.; Schwarz, H.; Rue, C.; Armentrout, P. B. Experimental and Theoretical Studies of Vanadium Sulfide Cation. J. Phys. Chem. A 1998, 102, 10060.
37. (b) Rue, C.; Armentrout, P. B.; Kretzschmar, I.; Schröder, D.; Harvey, J. N.; Schwarz, H. Kinetic-energy dependence of competitive spin-allowed and spin-forbidden reactions. J. Chem. Phys. 1999, 110, 7858.
38. +: A guided ion beam study. J. Chem. Phys. 1995, 102, 754.
39. th Row. Dissertation, TU Berlin D83; Shaker Verlag: Aachen, 1999.
40. Yoshizawa; K.; Shiota, Y.; Yamabe, T. Intrinsic reaction coordinate analysis of the conversion of methane to methanol by an iron-oxo species: A study of crossing seams of potential energy surfaces. J. Chem. Phys. 1999, 111, 538 and references therein.
41. Yoshizawa, K.; Shiota, Y.; Yamabe, T. Reaction Pathway for the Direct Benzene Hydroxylation by Iron-Oxo Species. J. Am. Chem. Soc. 1999, 121, 147.
42. +. Helv. Chim. Acta 1999, 82, 1784.
43. Yoshizawa; K.; Shiota, Y.; Yamabe, T. Reaction Pathway for the Direct Benzene Hydroxylation by Iron-Oxo Species. Organometallics 1998, 17, 2825.
44. +: A case of two-state reactivity? Inorg. Chim. Acta 1997, 259, 227.
45. Poli, R. Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure. Chem. Rev. 1996, 96, 2135.
46. Toy, P. H.; Newcomb, M.; Hollenberg, P. F. Hypersensitive Mechanistic Probe Studies of Cytochrome P450-Catalyzed Hydroxylation Reactions. Implications of the Cationic Pathway. J. Am. Chem. Soc. 1998, 120, 7719 and references therein.
47. Jin, N.; Groves, J. T. Unusual Kinetic Stability of a Ground-State Singlet Oxomanganese(V) Porphyrin. Evidence for a Spin State Crossing Effect. J. Am. Chem. Soc. 1999, 121, 2923.
48. Linde, C.; Akermark, B.; Norrby, P.-O.; Svensson, M. Timing is Critical: Effect of Spin Changes on the Diastereoselectivity in Mn-(salen)-Catalyzed Epoxidation. J. Am. Chem. Soc. 1999, 121, 5083.
49. Grissom, C. B. Magnetic Field Effects in Biology. Chem. Rev. 1995, 95, 3.
50. White, R. E.; Miller, J. P.; Favreau, L. V.; Bhattacharyya, A. Stereochemical Dynamics of Aliphatic Hydroxylation by Cytochrome P-450. J. Am. Chem. Soc. 1986, 108, 6024.
51. Groves, J. T. Key Elements of the Chemistry of Cyctochrome P-450. The Oxygen Rebound Mechanisms. J. Chem. Educ. 1985, 62, 928.
52. Mancester, J. J.; Dinnocenzo, J. P.; Higgins, L.; Jones, J. P. A New Mechanistic Probe for Cytochrome P450: An Application of Isotope Effect Profiles. J. Am. Chem. Soc. 1997, 119, 5069 and references therein.