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Volumn 130, Issue 50, 2008, Pages 16898-16907

Theoretical and experimental studies on the mechanism of norbornadiene Pauson-Khand cycloadducts photorearrangement. Is there a pathway on the excited singlet potential energy surface?

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOADDITION; ENERGY BARRIERS; GROUND STATE; HYDROCARBONS; MOLECULAR PHYSICS; POTENTIAL ENERGY; POTENTIAL ENERGY SURFACES; QUANTUM CHEMISTRY; QUENCHING; RATE CONSTANTS;

EID: 58049194288     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja802666v     Document Type: Article
Times cited : (5)

References (66)
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    • The mechanism of this type of reaction has been the subject of some controversy
    • (b) Marchueta, I.; Olivella, S.; Solà, L.; Moyano, A.; Pericàs, M. A.; Riera, A. Org. Lett. 2001, 3, 3197. The mechanism of this type of reaction has been the subject of some controversy.
    • (2001) Org. Lett , vol.3 , pp. 3197
    • Marchueta, I.1    Olivella, S.2    Solà, L.3    Moyano, A.4    Pericàs, M.A.5    Riera, A.6
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    • Selected reviews:(a) Blanco-Urgoiti, J.; Anorbe, L.; Perez-Serrano, L.; Dominguez, G.; Perez-Castells, J. Chem. Soc. Rev. 2004, 33, 32.
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    • 58049192010 scopus 로고    scopus 로고
    • For the excited states, we follow the conventional notation of designating the lowest electronic excited states of conjugated α,β-unsaturated ketones in terms of orbital occupancy of the nonbonding lone pair orbital (n) of the oxygen atom and the highest occupied (π) and lowest unoccupied (π*) orbitals of the ground-state π-system and the spin multiplicity singlet or triplet
    • For the excited states, we follow the conventional notation of designating the lowest electronic excited states of conjugated α,β-unsaturated ketones in terms of orbital occupancy of the nonbonding lone pair orbital (n) of the oxygen atom and the highest occupied (π) and lowest unoccupied (π*) orbitals of the ground-state π-system and the spin multiplicity (singlet or triplet).
  • 35
    • 58049207407 scopus 로고    scopus 로고
    • At the CASPT2 level of theory the vertical excitation energy of the 1(ππ*) state was calculated to be 149.5 kcal/mol see Table S32, Supporting Information, Therefore, this excited singlet state was not further considered in this study
    • 1(ππ*) state was calculated to be 149.5 kcal/mol (see Table S32, Supporting Information). Therefore, this excited singlet state was not further considered in this study.
  • 36
    • 58049207403 scopus 로고    scopus 로고
    • The common computational strategy to perform single-point CASPT2 calculations at CASSCF optimized geometries is only valid when the PESs described at both levels of theory behave more or less parallel with a constant relative influence of dynamic electron correlation. Therefore, the geometry optimization of these stationary points should be performed at the CASPT2 level of theory. Unfortunately, this type of calculation is still not practical for systems as large as C10H10O. To clarify this issue, the stationary points on the singlet ground-state PES were optimized by means of density functional theory calculations by using the spin-unrestricted version of the B3LYP functional14 with the 6-311G(d,p) basis set. Nowadays it is generally accepted that the B3LYP functional accounts for most of the dynamic electron correlation energy, and therefore one would expect a reasonable description of the PES region where the bond breaking/making processes take place
    • -1 below the energies of the transition states found for the C4-C8 bond breaking and C2-C10 bond forming, respectively. Therefore, the B3LYP calculations predict the bis-allyl diradical to be a shallow minimum on the singlet ground-state PES.
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    • Compound 1b (R = TMS, R′ = H) did not rearrange or decompose in o-dichlorobenzene at reflux (195°C). When 1b is heated in a solution of dioctyl ether at 250°C, it slowly decomposes, but 2b could not be detected in the reaction crude product.
    • Compound 1b (R = TMS, R′ = H) did not rearrange or decompose in o-dichlorobenzene at reflux (195°C). When 1b is heated in a solution of dioctyl ether at 250°C, it slowly decomposes, but 2b could not be detected in the reaction crude product.
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    • Gaussian, Inc, Wallingford, CT
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.