Through-Bond Interactions in the Diradical Intermediates Formed in the Rearrangements of Bicyclo[n.m.0]alkatetraenes

Description:

Article on through-bond interactions in the diradical intermediates formed in the rearrangements of bicyclo[n.m.0]alkatetraenes.

Creator(s):
Creation Date: September 24, 2010
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Creator (Author):
Lovitt, Charity Flener

University of North Texas

Creator (Author):
Dong, Hao

University of North Texas

Creator (Author):
Hrovat, David A.

University of North Texas

Creator (Author):
Gleiter, Rolf

Heidelberg University

Creator (Author):
Borden, Weston T., 1943-

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
Date(s):
  • Creation: September 24, 2010
Description:

Article on through-bond interactions in the diradical intermediates formed in the rearrangements of bicyclo[n.m.0]alkatetraenes.

Degree:
Department: Chemistry
Note:

Abstract: The intermediates and transition structures in the degenerate thermal rearrangements of bicyclo[4.4.0]deca-2,4,7,9-tetraene (1c), bicyclo[5.5.0]dodeca-2,4,8,10-tetraene(11b), and bicyclo[5.4.0]undeca-2.4.8.10-tetraene (14) have been located by (U)B3LYP/6-31G(d) calculations. The singlet-triplet energy differences (∆Est) in the diradical intermediates (tricyclo[4.4.0.02,7]deca-3,8-dien-5,10-diyl (2c), tricyclo[5.5.0.05,11]dodeca-2,8-dien-4,10-diyl (12b), and tricyclo[5.4.0.05,11]undeca-2,8-dien-4,10-diyl(15)) have been computed, using both UB3LYP and (6/6)CASPT2 calculations. ∆Est in 2c, in which a four-membered ring is anti-bridged by two allylic radicals, is computed to be larger by a factor of 5 than ∆Est in 15, in which the anti-bridged ring is five-membered, and by a factor of 10 than that in 12b, in which the anti-bridged ring is six-membered. The reasons for the much larger interaction between two allylic radicals through the bonds of the four-membered ring in 2c than through the bonds of the five-membered ring in 15 or the six-membered ring in 12b are discussed, and the consequences of the large, through-bond stabilization of the singlet state of 2c are described.

Note:

Reprinted with permission from the Journal of the American Chemical Society. Copyright 2010 American Chemical Society.

Physical Description:

8 p.

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Subject(s):
Keyword(s): diradical intermediates | through-bond interactions
Source: Journal of the American Chemical Society, 2010, Washington DC: American Chemical Society, pp. 14617-14624
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja106329t
  • ARK: ark:/67531/metadc71806
Resource Type: Article
Format: Text
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 132
Page Start: 14617
Page End: 14624
Pages: 8
Peer Reviewed: Yes