Isomerization of an η3-allyl to an (E)-1-propenyl in (C5Me5)(C5Me4CH2)tiC3H5: Mechanism, kinetics, and thermodynamics

Journal of the American Chemical Society

Volumn 120, Issue 12, 1998, Pages 2854-2861

  Brinkmann, Peter H P ^a   Luinstra, Gerrit A ^a   Saenz, Alejandro ^a  

^a UNIVERSITY OF KONSTANZ   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CHEMICAL REACTION KINETICS; ENTROPY; ISOMERISM; MOLECULAR INTERACTION; SYNTHESIS; THERMODYNAMICS;

EID: 0032053558     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja972867b     Document Type: Article

References (32)

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2. If this occurs intermolecularly through reaction of an alkane with the fulvene entity, a metal alkyl is produced. This has been considered a key step toward the functionalization of alkanes. It is the reverse of the formation of tetramethyl fulvenes from coordinating permethyl Cp by methyl group hydrogen abstraction, a common feature of the thermolysis of early transition metal and lanthanide permethylmetallocene alkyls; see references cited in ref 1.
3. II; see, e.g.: Hoveyda, A. H.; Morken, J. P. Angew. Chem. 1996, 108, 1378. Also, from a "commercial" point of view, this is an interesting reaction: Aldrich prices for allyl bromide ≈ $0.10/g and (E)-BrCH=CHMe ≈ $30/g would make this an interesting conversion.
4. 3B. (a) Thiele, K. H.; Zdunneck, R. J. Organomet. Chem. 1965, 4, 10. (b) Topchiev, A. V.; Paushjin, M. Y.; Prokhorova, A. A. Dokl. Akad. Nauk. SSSR 1959, 129, 598.
5. 3B. (a) Thiele, K. H.; Zdunneck, R. J. Organomet. Chem. 1965, 4, 10. (b) Topchiev, A. V.; Paushjin, M. Y.; Prokhorova, A. A. Dokl. Akad. Nauk. SSSR 1959, 129, 598.
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8. 6). However, no characteristic features were found that allow rate determinations in the time-dependent spectra.
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21. The analytical expression contains a sum of exponential terms. If the exponents differ largely in magnitude, the finite precision of a computer will easily lead to numerical inaccuracies in the evaluation of sums of this type. See also: Matsen, F. A.; Franklin, J. L. J. Am. Chem. Soc. 1950, 72, 3337. (b) McLaughin, E.; Rozett, R. W. J. Chem. Educ. 1972, 49, 482. (c) Wei, J.; Prater, C. D. Adv. Catal. 1962, 13, 203ff. Benson, S. W. The Foundation of Kinetics McGraw-Hill: New York, 1953.
22. The analytical expression contains a sum of exponential terms. If the exponents differ largely in magnitude, the finite precision of a computer will easily lead to numerical inaccuracies in the evaluation of sums of this type. See also: Matsen, F. A.; Franklin, J. L. J. Am. Chem. Soc. 1950, 72, 3337. (b) McLaughin, E.; Rozett, R. W. J. Chem. Educ. 1972, 49, 482. (c) Wei, J.; Prater, C. D. Adv. Catal. 1962, 13, 203ff. Benson, S. W. The Foundation of Kinetics McGraw-Hill: New York, 1953.
23. The analytical expression contains a sum of exponential terms. If the exponents differ largely in magnitude, the finite precision of a computer will easily lead to numerical inaccuracies in the evaluation of sums of this type. See also: Matsen, F. A.; Franklin, J. L. J. Am. Chem. Soc. 1950, 72, 3337. (b) McLaughin, E.; Rozett, R. W. J. Chem. Educ. 1972, 49, 482. (c) Wei, J.; Prater, C. D. Adv. Catal. 1962, 13, 203ff. Benson, S. W. The Foundation of Kinetics McGraw-Hill: New York, 1953.
24. The analytical expression contains a sum of exponential terms. If the exponents differ largely in magnitude, the finite precision of a computer will easily lead to numerical inaccuracies in the evaluation of sums of this type. See also: Matsen, F. A.; Franklin, J. L. J. Am. Chem. Soc. 1950, 72, 3337. (b) McLaughin, E.; Rozett, R. W. J. Chem. Educ. 1972, 49, 482. (c) Wei, J.; Prater, C. D. Adv. Catal. 1962, 13, 203ff. Benson, S. W. The Foundation of Kinetics McGraw-Hill: New York, 1953.
25. 3 and a much poorer overall fit result.
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31. 3-hydridized carbon; see ref 16.
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