| Description: | This article discusses through-bond interactions. 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. |
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| Creator(s): | |
| Creation Date: | September 24, 2010 |
| Partner(s): |
UNT College of Arts and Sciences
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| Collection(s): |
UNT Scholarly Works
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| Usage: |
Total Uses: 66
Past 30 days: 3
Yesterday: 0
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| Creator (Author): |
Lovitt, Charity Flener
University of North Texas |
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| Creator (Author): |
Dong, Hao
University of North Texas |
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| Creator (Author): |
Hrovat, David A.
University of North Texas |
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| Creator (Author): |
Gleiter, Rolf
Heidelberg University |
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| Creator (Author): |
Borden, Weston Thatcher
University of North Texas |
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| Publisher Info: |
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
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| Original Creation Date: | September 24, 2010 | |
| Description: | This article discusses through-bond interactions. 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. |
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| Degree: |
Department:
Chemistry
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| Note: |
Reprinted with permission from the Journal of the American Chemical Society. Copyright 2010 American Chemical Society. |
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| Physical Description: |
8 p. |
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| Subject(s): |
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| 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
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| Collection: |
UNT Scholarly Works
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| Identifier: |
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| 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
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