Benzylchlorocarbene: Origins of Arrhenius Curvature in the Kinetics of the 1,2-H Shift Rearrangement

Journal of Organic Chemistry

Volumn 63, Issue 9, 1998, Pages 3010-3016

  Merrer, Dina C ^a   Moss, Robert A ^a   Liu, Michael T H ^b   Banks, J T ^b,d   Ingold, Keith U ^c  

^a RUTGERS UNIVERSITY   (United States)

^b UNIVERSITY OF PRINCE EDWARD ISLAND   (Canada)

^c NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^d LAKEHEAD UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000865948     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972198k     Document Type: Article

References (37)

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6. 5
7. Storer, J. W.; Houk, K. N. J. Am. Chem. Soc. 1993, 115, 10426. However, the computational results indicate that, above 200 K, the classical rate exceeds that due to tunneling, and the KIE decreases with increasing temperature.
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23. 2 using 10 mM [2] in isooctane.
24. Polar solvents stabilize the "polar" 1,2-H shift transition state: see ref 13b, and Sugiyama, M. J.; Celebi, S.; Platz, M. S. J. Am. Chem. Soc. 1992, 114, 966. The more negative ΔS‡ observed in the polar solvents may reflect enhanced solvation of the H-shift transition state.
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27. -1 in MCH at -90°C (this work). The rate constants were obtained by LFP, following the rate of decay of BCC as a function of [2].
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30. -1.
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33. For a description of this installation, see Moss, R. A.; Shen, S.; Hadel, L. M.; Kmiecik-Lawrynowicz, G.; Wlostoweka, J.; Krogh- Jespersen, K. J. Am. Chem. Soc. 1987, 109, 4341 and Moss, R. A.; Xue, S.; Liu, W.; Krogh-Jespersen, K. J. Am. Chem. Soc. 1996, 118, 12588.
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