Exchange-enhanced h-abstraction reactivity of high-valent nonheme iron(IV)-oxo from coupled cluster and density functional theories

Journal of Physical Chemistry Letters

Volumn 1, Issue 10, 2010, Pages 1533-1540

  Chen, Hui ^a   Lai, Wenzhen ^a   Shaik, Sason ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

B3LYP CALCULATIONS; COMPUTATIONAL STUDIES; COUPLED CLUSTERS; DENSITY FUNCTIONAL THEORY METHODS; DFT METHOD; FUNCTIONALS; GEOMETRY OPTIMIZATION; H-ABSTRACTION; HIGH-VALENT IRONS; HYDROGEN ABSTRACTION; NONHEME; NONHEME IRON; QUINTET STATE; SPIN STATE; STATE TRANSITIONS;

ABSTRACTING; COMPRESSED AIR MOTORS; METHANE; SPIN DYNAMICS;

DENSITY FUNCTIONAL THEORY;

EID: 77952713408     PISSN: None     EISSN: 19487185     Source Type: Journal    
DOI: 10.1021/jz100359h     Document Type: Article

References (47)

1. Costas, M.; Mehn, M. P.; Jensen, M. P.; Que, L., Jr. Dioxygen Activation at Mononuclear Nonheme Iron Active Sites: Enzymes, Models, and Intermediates Chem. Rev. 2004, 104, 939-986
2. Solomon, E. I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.; Lee, S.-K.; Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S.; Zhou, J. Geometric and Electronic Structure/Function Correlations in Non-Heme Iron Enzymes Chem. Rev. 2000, 100, 235-349
3. See special issue and accounts therein: Nam, W. Dioxygen Activation by Metalloenzymes and Models Acc. Chem. Res. 2007, 40, 465-465
4. 57Fe Mössbauer Spectroscopy: Monitoring Changes of an Iron-Containing Active Site during a Biochemical Reaction Inorg. Chem. 2005, 44, 742-757
5. Hoffart, L. M.; Barr, E. W.; Guyer, R. B.; Bollinger, J. M., Jr.; Krebs, C. Direct Spectroscopic Detection of a C-H-cleaving High-Spin Fe(IV) Complex in a Prolyl-4-hydroxylase Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 14738-14743
6. Galonić, D. P.; Barr, E. W.; Walsh, C. T.; Bollinger, J. M., Jr.; Krebs, C. Two Interconverting Fe(IV) Intermediates in Aliphatic Chlorination by the Halogenase CytC3 Nat. Chem. Biol. 2007, 3, 113-116
7. Eser, B. E.; Barr, E. W.; Frantom, P. A.; Saleh, L.; Bollinger, J. M., Jr.; Krebs, C.; Fitzpatrick, P. F. Direct Spectroscopic Evidence for a High-Spin Fe(IV) Intermediate in Tyrosine Hydroxylase J. Am. Chem. Soc. 2007, 129, 11334-11335
8. Krebs, C.; Fujimori, D. G.; Walsh, C. T.; Bollinger, J. M., Jr. Non-Heme Fe(IV)-Oxo Intermediates Acc. Chem. Res. 2007, 40, 484-492
9. Price, J. C.; Barr, E. W.; Glass, T. E.; Krebs, C.; Bollinger, J. M., Jr. Evidence for Hydrogen Abstraction from C1 of Taurine by the High-Spin Fe(IV) Intermediate Detected during Oxygen Activation by Taurine: α-Ketoglutarate Dioxygenase (TauD) J. Am. Chem. Soc. 2003, 125, 13008-13009
10. IVO Complexes That Can Oxidize the C-H Bonds of Cyclohexane at Room Temperature J. Am. Chem. Soc. 2004, 126, 472-473
11. Oh, N. Y.; Suh, Y.; Park, M. J.; Seo, M. S.; Kim, J.; Nam, W. Mechanistic Insight into Alcohol Oxidation by High-Valent Iron-Oxo Complexes of Heme and Nonheme Ligands Angew. Chem., Int. Ed. 2005, 44, 4235-4239
12. Klinker, E. J.; Shaik, S.; Hirao, H.; Que, L., Jr. A Two-State Reactivity Model Explains Unusual Kinetic Isotope Effect Patterns in C-H Bond Cleavage by Nonheme Oxoiron(IV) Complexes Angew. Chem., Int. Ed. 2009, 48, 1291-1295
13. 2+: An Oxidant More Powerful than P450? J. Am. Chem. Soc. 2005, 127, 8026 - 8027.
14. Hirao, H.; Kumar, D.; Que, L., Jr.; Shaik, S. Two-State Reactivity in Alkane Hydroxylation by Nonheme Iron-Oxo Complexes J. Am. Chem. Soc. 2006, 128, 8590-8606
15. IV=O Oxidants Chem.-Eur. J. 2008, 14, 1740-1756
16. Shaik, S.; Hirao, H.; Kumar, D. Reactivity of High-Valent Iron-Oxo Species in Enzymes and Synthetic Reagents: A Tale of Many States Acc. Chem. Res. 2007, 40, 532-542
17. Janardanan, D.; Wang, Y.; Schyman, P.; Que, L., Jr.; Shaik, S. Fundamental Role of Exchange-Enhanced Reactivity in C-H Activation by S = 2 Oxo Iron(IV) Complexes. Angew. Chem., Int. Ed. 2010, 49, 3342 - 3345.
18. 2+ J. Phys. Chem. C 2007, 111, 12397-12406
19. Bernasconi, L.; Louwerse, M. J.; Baerends, E. J. The Role of Equatorial and Axial Ligands in Promoting the Activity of Non-Heme Oxidoiron(IV) Catalysts in Alkane Hydroxylation Eur. J. Inorg. Chem. 2007, 3023-3033
20. de Visser, S. P. Propene Activation by the Oxo-Iron Active Species of Taurine/α-Ketoglutarate Dioxygenase (TauD) Enzyme. How Does the Catalysis Compare to Heme-Enzymes? J. Am. Chem. Soc. 2006, 128, 9813 - 9824.
21. Ye, S. F.; Neese, F. Quantum Chemical Studies of C-H Activation Reactions by High-Valent Nonheme Iron Centers Curr. Opin. Chem. Biol. 2009, 13, 89-98
22. England, J.; Martinho, M.; Farquhar, E. R.; Frisch, J. R.; Bominaar, E. L.; Münck, E.; Que, L., Jr. A Synthetic High-Spin Oxoiron(IV) Complex: Generation, Spectroscopic Characterization, and Reactivity Angew. Chem., Int. Ed. 2009, 48, 3622-3626
23. Neese, F. Prediction of Molecular Properties and Molecular Spectroscopy with Density Functional Theory: From Fundamental Theory to Exchange-Coupling Coord. Chem. Rev. 2009, 253, 526-563
24. Here we need to point out that we are not trying to model the accurate reaction barriers comparable to experimental results for these studied reactions, since there are several issues not addressed yet in our RCCSD(T) calculations, such as relativistic effect, geometric accuracy (as shown in Figure 1), solvent effect, zero point energies, and thermal corrections.
25. Grimme, S. Semiempirical GGA-Type Density Functional Constructed with a Long-Range Dispersion Correction J. Comput. Chem. 2006, 27, 1787-1799
26. Karton, A.; Tarnopolsky, A.; Lamère, J.-F.; Schatz, G. C.; Martin, J. M. L. Highly Accurate First-Principles Benchmark Data Sets for the Parametrization and Validation of Density Functional and Other Approximate Methods. Derivation of a Robust, Generally Applicable, Double-Hybrid Functional for Thermochemistry and Thermochemical Kinetics J. Phys. Chem. A 2008, 112, 12868-12886
27. Iikura, H.; Tsuneda, T.; Yanai, T.; Hirao, K. A Long-Range Correction Scheme for Generalized-Gradient-Approximation Exchange Functionals J. Chem. Phys. 2001, 115, 3540-3544
28. Sousa, S. F.; Fernandes, P. A.; Ramos, M. J. General Performance of Density Functionals J. Phys. Chem. A 2007, 111, 10439-10452
29. Cramer, C. J.; Truhlar, D. G. Density Functional Theory for Transition Metals and Transition Metal Chemistry Phys. Chem. Chem. Phys. 2009, 11, 10757-10816
30. Zhao, Y.; Truhlar, D. G. Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions J. Phys. Chem. A 2005, 109, 5656-5667
31. Zhao, Y.; Lynch, B. J.; Truhlar, D. G. Development and Assessment of a New Hybrid Density Functional Model for Thermochemical Kinetics J. Phys. Chem. A 2004, 108, 2715-2719
32. Cohen, A. J.; Mori-Sánchez, P.; Yang, W. T. Insights into Current Limitations of Density Functional Theory Science 2008, 321, 792-794
33. Mori-Sánchez, P.; Cohen, A. J.; Yang, W. T. Many-Electron Self-Interaction Error in Approximate Density Functionals J. Chem. Phys. 2006, 125, 201102
34. The usage of double-hybrid functional is restricted in the current first-row transition metal-containing systems because of their very high HF exchange component, which makes the proceeding SCF calculation before MP2 vulnerable to convergence failure as shown in Table 2.
35. Kang, Y.; Chen, H.; Jeong, Y. J.; Lai, W. Z.; Bae, E. H.; Shaik, S.; Nam, W. Enhanced Reactivities of Iron(IV)-Oxo Porphyrin π-Cation Radicals in Oxygenation Reactions by Electron-Donating Axial Ligands Chem.-Eur. J. 2009, 15, 10039-10046
36. Takahashi, A.; Kurahashi, T.; Fujii, H. Effect of Imidazole and Phenolate Axial Ligands on the Electronic Structure and Reactivity of Oxoiron(IV) Porphyrin π-Cation Radical Complexes: Drastic Increase in Oxo-Transfer and Hydrogen Abstraction Reactivities Inorg. Chem. 2009, 48, 2614-2625
37. Shaik, S.; Cohen, S.; Wang, Y.; Chen, H.; Kumar, D.; Thiel, W. P450 Enzymes: Their Structure, Reactivity, and Selectivity-Modeled by QM/MM Calculations Chem. Rev. 2010, 110, 949-1017
38. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A. Gaussian 09, revision A.02; Gaussian, Inc., Wallingford, CT, 2009.
39. Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy Phys. Chem. Chem. Phys. 2005, 7, 3297-3305
40. Knowles, P. J.; Hampel, C.; Werner, H.-J. Coupled Cluster Theory for High Spin, Open Shell Reference Wave Functions J. Chem. Phys. 1993, 99, 5219-5227
41. Watts, J. D.; Gauss, J.; Bartlett, R. J. Coupled-Cluster Methods with Noniterative Triple Excitations for Restricted Open-Shell Hartree-Fock and Other General Single Determinant Reference Functions. Energies and analytical gradients J. Chem. Phys. 1993, 98, 8718-8733
42. Adler, T. B.; Knizia, G.; Werner, H.-J. A Simple and Efficient CCSD(T)-F12 Approximation J. Chem. Phys. 2007, 127, 221106
43. Knizia, G.; Adler, T. B.; Werner, H.-J. Simplified CCSD(T)-F12 Methods: Theory and Benchmarks J. Chem. Phys. 2009, 130, 054104
44. Werner, H.-J.; Knowles, P. J.; Lindh, R.; Manby, F. R.; Schütz, M.; Celani, P.; Korona, T.; Mitrushenkov, A.; Rauhut, G.; Adler, T. B. MOLPRO, version 2009.1, a package of ab initio programs; see http://www.molpro.net.
45. Musial, M.; Bartlett, R. J. Critical Comparison of Various Connected Quadruple Excitation Approximations in the Coupled-Cluster Treatment of Bond Breaking J. Chem. Phys. 2005, 122, 224102
46. Ge, Y. B.; Gordon, M. S.; Piecuch, P. Breaking Bonds with the Left Eigenstate Completely Renormalized Coupled-Cluster Method J. Chem. Phys. 2007, 127, 174106
47. Wloch, M.; Gour, J. R.; Piecuch, P. Extension of the Renormalized Coupled-Cluster Methods Exploiting Left Eigenstates of the Similarity- Transformed Hamiltonian to Open-Shell Systems: A Benchmark Study J. Phys. Chem. A 2007, 111, 11359-11382