Dynamic processes in [16]annulene: Möbius bond-shifting routes to configuration change

Journal of the American Chemical Society

Volumn 128, Issue 51, 2006, Pages 16692-16700

  Pemberton, Ryan P ^a   McShane, Colleen M ^a   Castro, Claire ^a   Karney, William L ^a  

^a UNIVERSITY OF SAN FRANCISCO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; CONFORMATIONS; ISOMERS; PROBABILITY DENSITY FUNCTION; THERMODYNAMIC PROPERTIES; TOPOLOGY;

AUTOMERIZATION; DYNAMIC PROCESSES; ENERGY BARRIERS; TRANSITION STATES;

OLEFINS;

ANNULENE DERIVATIVE;

AB INITIO CALCULATION; ARTICLE; CHEMICAL BINDING; CIS TRANS ISOMERISM; CONFORMATIONAL TRANSITION; DENSITY FUNCTIONAL THEORY; ISOMERIZATION; MATHEMATICAL COMPUTING; MEMBRANE STRUCTURE; MOBIUS BOND; THERMAL ANALYSIS;

COMPUTER SIMULATION; MACROCYCLIC COMPOUNDS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR CONFORMATION; POLYCYCLIC HYDROCARBONS, AROMATIC;

EID: 33845979150     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja066152x     Document Type: Article

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66. 12 Single-point energies using CCSDT)/6-31G* increased this barrier to 19.6 kcal/mol as compared to the experimental barrier (17.4 kcal/mol. Table 2).
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68. Re-optimizing the [12]annulene bond-shifting transition state and recomputing the frequencies using UBH&HLYP/TZ decreases the relative energy by 3.5 kcal/mol, yielding a barrier that deviates by only 0.7 kcal/mol from the experimental one.
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