TY - JOUR
T1 - Inversion barrier of corannulene. A benchmark for bowl-to-bowl inversions in fullerene fragments
AU - Biedermann, P. U.
AU - Pogodin, S.
AU - Agranat, I.
PY - 1999
Y1 - 1999
N2 - In a systematic ab initio study, the Hartree-Fock, B3LYP density functional, and MP2 methods are employed to calculate the bowl-to-bowl inversion barrier of corannulene (1). Basis sets ranging from a minimal basis (STO-3G) to a double polarized valence triple-ζ basis (6-311G(2d,2p)) were used. In comparison with experimental data, it was found that inclusion of dynamic electron correlation (e.g., B3LYP) and a 6-311G** basis set (or other basis sets with similar complexity) are essential for quantitatively correct results. At B3LYP/6-311G**, ΔG(+)298 = 44.9 kJ/mol. Thermal corrections to Gibbs energy of activation were of minor importance in the relevant range of temperatures. Inversion barriers (ΔE(+)(Tot)) of the bowl- shaped fullerene fragments C26H12 4 and C30H12 5 and the chiral C30H12 6 are predicted to be 28.0, 199.4, and 277.3 kJ/mol, respectively, at B3LYP/6-311G**. Predicted enthalpies of formations and strain energies are also discussed.
AB - In a systematic ab initio study, the Hartree-Fock, B3LYP density functional, and MP2 methods are employed to calculate the bowl-to-bowl inversion barrier of corannulene (1). Basis sets ranging from a minimal basis (STO-3G) to a double polarized valence triple-ζ basis (6-311G(2d,2p)) were used. In comparison with experimental data, it was found that inclusion of dynamic electron correlation (e.g., B3LYP) and a 6-311G** basis set (or other basis sets with similar complexity) are essential for quantitatively correct results. At B3LYP/6-311G**, ΔG(+)298 = 44.9 kJ/mol. Thermal corrections to Gibbs energy of activation were of minor importance in the relevant range of temperatures. Inversion barriers (ΔE(+)(Tot)) of the bowl- shaped fullerene fragments C26H12 4 and C30H12 5 and the chiral C30H12 6 are predicted to be 28.0, 199.4, and 277.3 kJ/mol, respectively, at B3LYP/6-311G**. Predicted enthalpies of formations and strain energies are also discussed.
UR - http://www.scopus.com/inward/record.url?scp=0032925470&partnerID=8YFLogxK
U2 - 10.1021/jo9900174
DO - 10.1021/jo9900174
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AN - SCOPUS:0032925470
SN - 0022-3263
VL - 64
SP - 3655
EP - 3662
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 10
ER -