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Quantum chemistry investigation of electronic structure and NMR spectral characteristics for fluorides of dialkylamidosulfoxylic acids and related compounds
Author(s) -
Rozhenko A. B.,
Schoeller W. W.,
Kozel V. N.,
Pashinnik V. E.,
Shermolovich Yu. G.
Publication year - 2009
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2466
Subject(s) - chemistry , delocalized electron , ab initio , chemical shift , computational chemistry , quantum chemical , crystallography , fluorine , carbon 13 nmr , stereochemistry , molecule , organic chemistry
The parent (H 2 NSF) and N , N ‐dialkyl‐substituted fluorides of amidosulfoxylic acid (R 2 NSF, RMe or R 2 NMorph) as well as the related compounds XSF (XCH 3 , OH, F, SiH 3 , PH 2 , SH, Cl) have been investigated with quantum chemical calculations at the ab initio (MP2) level of approximation. The geometries, electronic structures, molecular orbital (MO) energies and NMR chemical shift values have been calculated to evaluate the role and extent of the polarization and delocalization effects in forming of the high‐field fluorine NMR resonances within the series of interest. The δF magnitudes for all investigated fluorides of amidosulfoxylic acid as well as the δN value calculated for Me 2 NSF are in the good agreement with the 19 F and 14 N NMR chemical shift values measured experimentally. For the parent compounds, H 2 NSF and H 2 NSO 2 F, the orientation of principal axes of the magnetic shielding tensors and the corresponding principal σ ii values along these axes have been qualitatively interpreted basing on the analysis of the MO interactions in the presence of the rotating magnetic field. Copyright © 2009 John Wiley & Sons, Ltd.