β-Hydride shift involvement in the acid catalysed decomposition of [(H₂O)₅Cr^III–C(CH₃)₂OH]²⁺

Abstract

Propene has been found to be a major product of the acid catalysed decomposition of [(H₂O)₅Cr^III–C(CH₃)₂OH]²⁺. It is proposed that this complex isomerizes via a β-hydride shift step to form [(H₂O)₅Cr^III–CH₂CH(CH₃)OH]²⁺ which decomposes via β-hydroxide elimination.

References

1. J. K. Kochi, Organometallic Mechanism and Catalysis, Academic Press, New York, 1978; R. A. Sheldon and J. K. Kochi, Metal Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981; M. Regitz and B. Geise(Editors), Houben-Weyl, Theime, Stuttgart, 1989, E19a; B. Cornlis and W. A. Hermann(Editors), Applied Homogeneous Catalysis with Organometallic Compounds, VCH, Weinheim, 1996.
2. D. Harman, in Free radicals, Aging and Degenerative Diseases, eds. J. E. Johnson, Jr., R. Walford, D. Harman and J. Miquel, Alan R. Liss, New York, 1986, p. 3.
3. D. Meyerstein, Interrelations Between Free Radicals and Metal Ions in Life Processes, eds. Astrid Sigel and Helmut Sigel, Marcel Dekker, New York, Basel, 1999, vol. 36, p. 41.
4. J. H. Espenson, Adv. Inorg. Bioinorg. Mech., 1982, 1, 1.
5. J. H. Espenson, Acc. Chem. Res., 1992, 25, 222.
6. H. Cohen and D. Meyerstein, Inorg. Chem., 1984, 23, 84.
7. A. Rotman, H. Cohen and D. Meyerstein, Inorg. Chem., 1985, 24, 4158.
8. G. W. Kirker, A. Bakac and J. H. Espenson, J. Am. Chem. Soc., 1982, 104, 1249.
9. H. Cohen and D. Meyerstein, Inorg. Chem., 1987, 26, 2342.
10. (a) H. Cohen and D. Meyerstein, Inorg. Chem., 1974, 13, 2434; (b) H. Cohen and D. Meyerstein, J. Chem. Soc., Dalton Trans., 1974, 2560.
11. H. Cohen and D. Meyerstein, J. Chem. Soc., Chem. Commun., 1972, 320.
12. H. Cohen, A. Feldman, R. Ish-Shalom and D. Meyerstein, J. Am. Chem. Soc., 1991, 113, 5292.
13. H. Cohen, D. Meyerstein, A. J. Shusterman and M. Weiss, J. Am. Chem. Soc., 1984, 106, 1876.
14. S. Goldstein, G. Czapski, H. Cohen, D. Meyerstein and S. Shaik, J. Chem. Soc., Faraday Trans. 1, 1993, 4045.
15. H. Cohen and D. Meyerstein, Angew Chem., 1985, 34, 779.
16. H. Cohen, R. van Eldik, W. Gaede, A. Gerhard, S. Goldstein, G. Czapski and D. Meyerstein, Inorg. Chim. Acta, 1994, 227, 57.
17. D. M. Singelton and J. K. Kochi, J. Am. Chem. Soc., 1967, 89, 6547; C. E. Castro and W. C. Kray, J. Am. Chem. Soc., 1963, 85, 2768; W. C. Kray and C. E. Castro, ibid., 1964, 86, 4603; J. K. Kochi and D. M. Singelton, J. Am. Chem. Soc., 1968, 90, 1582.
18. P. Huston, J. H. Espenson and A. Bakac, Inorg. Chem., 1991, 30, 4826.
19. N. Shaham, H. Cohen and D. Meyerstein, unpublished results.
20. W. Schmidt, J. H. Swinehart and H. Taube, J. Am. Chem. Soc., 1971, 93, 1117.
21. K. D. Asmus, H. Mockel and A. Henglein, J. Phys. Chem., 1973, 77, 1218.
22. P. Neta, G. R. Holdern and R. H. Schuler, J. Phys. Chem., 1971, 75, 449.