Bicyclo[2.2.1] hepta-2-ene-5-yl-7-ylium radical cation: A theoretical validation of a bishomoaromatic radical cation intermediate

Organic Letters

Volumn 5, Issue 8, 2003, Pages 1329-1331

  Larsson, Per Erik ^a   Salhi Benachenhou, Nessima ^a   Lunell, Sten ^a  

^a UPPSALA UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND; BICYCLO COMPOUND; BICYCLO[2.2.1]HEPT 2 EN 5 YL 7 YLIUM; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; ELECTRON; ELECTRON SPIN RESONANCE; HYBRID; POLARIZATION; THEORETICAL STUDY; VALIDATION PROCESS;

EID: 0141852326     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034272t     Document Type: Article

References (21)

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4. Three major hfcc components are taken from ref 2a, and the theoretical values are from ref 1.
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17. The most problematic aspect was that peculiar bonds and nonbonding orbitals were formed and that the α and β spin LS had several large differences. For example, the α-LS had a nonbonding orbital on C4 with an occupation of 0.45e, and the β-LS had a nonbonding orbital on C3 with an occupation of 0.36e.
18. The three-center search gives two well balanced LSs that have no large population in Rydberg (<0.003e) or antibonding orbitals (<0.089e).
19. This value was obtained by summing up the natural population charges for α and β spin for C2(-0.01, -0.02), C3(-0.05, 0.02), C7(-0.03, 0.00), H2(0.13, 0.13), H3(0.13, 0.14), and H7(0.14, 0.14). Another area where a substantial part of the positive charge is located is around C5-H5 (0.18): C5(-0.50, 0.42), H5(0.11, 0.14). The remaining charge (0.18) is delocalized.
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