A Becke3LYP/6-31G* study of the cope rearrangements of substituted 1,5- hexadienes provides computational evidence for a chameleonic transition state

Journal of the American Chemical Society

Volumn 121, Issue 45, 1999, Pages 10529-10537

  Hrovat, David A ^a   Beno, Brett R ^b,c   Lange, Holger ^b   Yoo, Hi Young ^b,d   Houk, K N ^b   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

^c BRISTOL MYERS SQUIBB   (United States)

^d AIR FORCE RESEARCH LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; NITRILE; VINYL DERIVATIVE;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL STRUCTURE; ENTHALPY; MOLECULAR STABILITY; REACTION ANALYSIS;

EID: 0033579184     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990476m     Document Type: Article

References (56)

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44. s transition structure. In the latter case the asymmetric UB3LYP transition structure was not located, but it is almost certainly higher in energy than the B3LYP transition structure.
45. 2h structure than the corresponding unrestricted calculation (i e., UB3LYP) for the parent Cope rearrangement. A more detailed analysis of the diradical and aromatic character of the variable Cope transition state has been performed by V. N. Staroverov and E. R. Davidson, submitted for publication.
46. 2h structure than the corresponding unrestricted calculation (i e., UB3LYP) for the parent Cope rearrangement. A more detailed analysis of the diradical and aromatic character of the variable Cope transition state has been performed by V. N. Staroverov and E. R. Davidson, submitted for publication.
47. 2h structure than the corresponding unrestricted calculation (i e., UB3LYP) for the parent Cope rearrangement. A more detailed analysis of the diradical and aromatic character of the variable Cope transition state has been performed by V. N. Staroverov and E. R. Davidson, submitted for publication.
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51. 4 caution against attaching any significance to this small deviation from additivity.
52. 2 = 0.94) that is nearly an equal mixture of singlet and triplet, UB3LYP almost certainly overestimates this bond length change. Through-bond interaction between the radical centers in the singlet should result in it having longer interallylic C-C bonds than the triplet.
53. 2 = 0) UB3LYP singlet cyclohexane-1,4-diyl would be lower in energy than the mixed state by an additional 2.6 kcal/ mol at this geometry.
54. 2 = 0 and the same energy as a restricted B3LYP calculation.
55. 9b
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