19-Electron intermediates in the ligand substitution of CpW(CO)3 · with a Lewis base

Journal of the American Chemical Society

Volumn 128, Issue 10, 2006, Pages 3152-3153

  Cahoon, James F ^a,b   Kling, Matthias F ^a,b,c   Sawyer, Karma R ^a,b   Frei, Heinz ^b   Harris, Charles B ^a,b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b LAWRENCE BERKELEY NATIONAL LABORATORY   (United States)

^c FOM INSTITUTE AMOLF   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

DICHLOROMETHANE; LEWIS ACID; LIGAND; METAL COMPLEX; ORGANOMETALLIC COMPOUND; TRANSITION ELEMENT;

ARTICLE; CHEMICAL REACTION KINETICS; DENSITY FUNCTIONAL THEORY; DIFFUSION; DIMERIZATION; ELECTRON; INFRARED SPECTROSCOPY; NEODYMIUM LASER;

EID: 33644948596     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja058258i     Document Type: Article

References (24)

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9. Cahoon, J. F.; Kling, M. F.; Schmatz, S.; Harris, C. B. J. Am. Chem. Soc. 2005, 127, 12555-12565.
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11. Virrels. I. G.; George, M. W.; Johnson, F. P. A.; Turner, J. J.; Westwell, J. R. Organometallics 1995, 14, 5203-5208.
12. DFT calculations have been carried out with Gaussian 03, revision B.04 (Frisch et al. Gaussian. Inc.: Pittsburgh, PA, 2003) applying the B3LYP functional and generic basis sets (LANL2DZ effective core potential for W and 6-31g(d) or 6-31+g(d) basis sets for all other atoms).
13. -1.
14. 3 and is formed by electron transfer from C to D.
15. 2 (see SI) indicate that C1 atom abstraction does not occur on the time scale of this experiment.
16. eff gives ΔG° = -2.4 ± 0.3 kcal/mol. Thus, the 19e species C is estimated to be 2-3 kcal/mol lower in energy than the 17e species B, likely due to an increase in bond order of 0.5 between the two species (see ref 3).
17. Errors correspond to 95% confidence intervals.
18. See the SI for a further discussion of disproportionation. The mechanism is a subject of continuing investigation in our laboratory.
19. 3 with B was directly observed in these studies and no evidence for species D was found.
20. B is the Boltzmann constant, h Planck's constant, T ambient temperature, and ΔG‡ the free energy of activation.
21. Rosa, A.; Baerends, E. J.; van Gisbergen, S. J. A.; van Lenthe, E.; Groeneveld, J. A.; Snijders, J. G. J. Am. Chem. Soc. 1999, 121, 10356-10365.
22. Dixon, A. J.; Gravelle, S. J.; Vandeburgt, L. J.; Poliakoff, M.; Turner, J. J.; Weitz, E. J. Chem. Soc., Chem. Commun. 1987, 1023-1025.
23. Note that concentration-dependent studies would not reveal whether the 19e species is an intermediate or transition state since the same kinetic behavior would be expected in both cases.
24. Haines, R. J.; Nolte, C. R. J. Organomet. Chem. 1970, 24, 725-736.