Abstract
Several studies suggest the importance of oxygen in the reactive intermediates for alkene metathesis,
M=CH2 + H2C=C*H2 ⇌ M=C*H2 + H2C=CH2 (1)
and of additional metal=oxo bonds in epoxidations,
For example: (1) catalytic amounts of oxygen were found to be essential for the formation of a stable metathesis catalyst in the WCl6/C2H5AlCl2 system1; (2) alkene epoxidation (and general oxidation) reactants such as CrCl2O2, OsO4, and SeO2 all have at least two oxygen ligands2; and (3) recently Osborn (personal communication) has described an Mo=oxo carbene as an effective metathesis catalyst. From extensive ab initio theoretical studies of Cr and Mo complexes, we show here that the presence of spectator metal–oxo bonds drives the formation of metallocycles, thereby playing a crucial role in the chemistry.
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References
Mocella, M. T., Rovner, R. & Muetterties, E. L. J. Am. chem. Soc. 98, 4689 (1976).
Sharpless, K. B., Teranishi, A. Y. & Bäckvall, J. E. J. Am. chem. Soc. 99, 3120 (1977).
Harding, L. B. & Goddard III, W. A. J. Am. chem. Soc. 99, 4520 (1977).
Benson, S. W. Thermochemical Kinetics (Wiley, New York, 1976).
Harding, L. B. & Goddard III, W. A. J. Am. chem. Soc. 97, 6293 (1975).
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Rappé, A., Goddard, W. Bivalent spectator oxo bonds in metathesis and epoxidation alkenes. Nature 285, 311–312 (1980). https://doi.org/10.1038/285311a0
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DOI: https://doi.org/10.1038/285311a0
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