ISSN:
0192-8651
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Biochemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
,
Informatik
Notizen:
The electronic states and barriers to internal rotation in allene (1a), 1-silaallene (2a), and 2-silaallene (3a) are investigated computationally using ab-initio molecular orbital methods. Planar geometries with two-, three-, and four-π-electron configurations have been considered as possible transition states (1b-3d). Structures have been optimized at the Hartree-Fock level with a small split valence basis set (3-21G) and higher level calculations with basis sets of split valence (6-31G) and split valence plus polarization function (6-31G*) quality include correlation energy estimates from Møller-Plesset second-and third-order perturbation theory. The electronic barrier to internal rotation in allene is estimated near 53 kcal/mol whereas the corresponding barriers in 1-silaallene and 2-silaallene are considerably smaller, ca. 35 and 20 kcal/mol, respectively. The transition states are predicted to possess bent geometries in all three molecules with open-shell singlet, three-π-electron configurations in 1 and 2 (1c, 2c) but a closed-shell singlet, two-π-electron configuration in 3 (3d).
Zusätzliches Material:
4 Tab.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/jcc.540030416
