N-H versus C-H activation of a pyrrole imine at {Cp*Ir}: A computational and experimental study

Organometallics

Volumn 25, Issue 26, 2006, Pages 5976-5978

  Davies, David L ^a   Donald, Steven M A ^b   Al Duaij, Omar ^a   Fawcett, John ^a   Little, Craig ^b   Macgregor, Stuart A ^b  

^a UNIVERSITY OF LEICESTER   (United Kingdom)

^b HERIOT WATT UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; COMPUTATIONAL METHODS; HYDROGEN BONDS; IRIDIUM COMPOUNDS; PROBABILITY DENSITY FUNCTION; REACTION KINETICS; SODIUM COMPOUNDS; THERMODYNAMIC PROPERTIES;

ACTIVATION OCCURS; PYRROLE IMINES; TRANSITION STATES;

AMINES;

EID: 33846343173     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om060863m     Document Type: Article

References (23)

1. Davies, D. L.; Al-Duaij, O.; Fawcett, J.; Giardiello, M.; Hilton, S. T.; Russell, D. R. Dalton Trans. 2003, 4132.
2. Davies, D. L.; Donald, S. M. A.; Macgregor, S. A. J. Am. Chem. Soc. 2005, 127, 13754.
3. Davies, D. L.; Donald, S. M. A.; Al-Duaij, O.; Macgregor, S. A.; Polleth, M. J. Am. Chem. Soc. 2006, 128, 4210.
4. (a) Privalov, T.; Linde, C.; Zetterberg, K.; Moberg, C. Organometallics 2005, 24, 885.
5. (b) Steinhoff, B. A.; Guzei, I. A.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 11268.
6. (c) Mueller, J. A.; Goller, C. P.; Sigman, M. S. J. Am. Chem. Soc. 2004, 126, 9724.
7. Ziatdinov, V. R.; Oxgaard, J.; Mironov, O. A.; Young, K. J. H.; Goddard, W. A.; Periana, R. A. J. Am. Chem. Soc. 2006, 128, 7404.
8. For reviews see for example: (a) Muller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675.
9. (b) Brunet, J.-J.; Neibecker, D. In Catalytic Hetero- functionalization; Togni, A., Grützmacher, H., Eds.; Wiley-VCH: Weinheim, Germany, 2001; p 91.
10. Bianchini, C.: Meli, A.; Vizza, F. Eur. J. Inorg. Chem. 2001, 43.
11. Macgregor, S. A. Organometallics 2001, 20, 1860.
12. Pittard, K. A.; Cundari, T. R.; Gunnoe, T. B.; Day, C. S.; Petersen, J. L. Organometallics 2005, 24, 5015.
13. Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 4108.
14. Gagné, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 114, 275.
15. (a) Ladipo, F. T.; Merola, J. S. Inorg. Chem. 1990, 29, 4172.
16. (b) Jones, W. D.; Dong, L.; Myers, A. W. Organometallics 1995, 14, 855.
17. (c) Morikita, T.; Hirano, M.; Sasaki, A.; Komiya, S. Inorg. Chim. Acta 1999, 291, 341.
18. (d) Lopez, C.; Baron, G.; Arevalo, A.; Munoz-Hernandez, M. A.; Garcia, J. J. J. Organomet. Chem. 2002, 664, 170.
19. (e) Hirano, M.; Onuki, K.; Kimura, Y.; Komiya, S. Inorg. Chim. Acta 2003, 352, 160.
20. Wang, X.; Lane, B. S.; Sames, D. J. Am. Chem. Soc. 2005, 127, 4996.
21. Frisch, M.; et al. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004. Calculations used the BP86 functional. Ir and Cl were described using the Stuttgart RECPs and the associated basis sets. 6-31G** basis sets were used for C, N, O, and H atoms. Zero-point energy corrections are included. See the Supporting Information for details.
22. +. H transfer to the remaining coordinated oxygen entailed activation barriers (relative to 3) of 21.2 kcal/mol (N-H activation) and 31.3 kcal/ mol (C-H activation). See the Supporting Information for details.
23. - and calculations on models of these species indicate the N-H bond activation product is the more stable one by 9.1 kcal/mol.