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Probing the Anomeric Effect in OCN Systems Theory vs. Experiment: MO‐ ab initio Calculations and a Structural‐Statistical Analysis
Author(s) -
Senderowitz Hanoch,
Aped Pinchas,
Fuchs Benzion
Publication year - 1990
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19900730807
Subject(s) - chemistry , anomeric effect , ab initio , anomer , computational chemistry , gaussian , molecule , basis set , gaussian orbital , series (stratigraphy) , electronic correlation , moiety , basis (linear algebra) , energy minimization , stereochemistry , density functional theory , geometry , organic chemistry , mathematics , paleontology , biology
A combined computational (MO ab initio ) and structural‐statistical study of molecules containing the OCN moiety is presented. Aminomethanol, the simplest member of this series, was computed using GAUSSIAN‐82 with the 3‐21G and 6‐31G* basis sets and with complete geometry optimization, as well as with MP3//6‐31G*. A set of carefully selected molecules containing the OCN unit was retrieved from the Cambridge Structural Database (CSD), and its structural parameters were analyzed according to an established procedure. Comparison between experimental and computational data was thus made possible. Results are consistent with the co‐existence of two unequal anomeric effects in this system: a strong n N ‐σ* CO anomeric interaction, and a weak n πO ‐σ* CN one. The ability of the two basis sets to reproduce the energies and structural characteristics of the stereoelectronic effects is assessed, including the significance of using polarization functions and the inclusion of correlation energy.