Document Detail


Density-functional computation of 53Cr NMR chemical shifts.
MedLine Citation:
PMID:  16602076     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
53Cr chemical shifts of CrO4(2-), Cr2O7(2-), CrO3X-, CrO2X2(X = F, Cl), and Cr(CO)5L (L = CO, PF3, CHNH2, CMeNMe2) are computed, using geometries optimized with the gradient-corrected BP86 density functional, at the gauge-including atomic orbitals (GIAO)-, BPW91-, and B3LYP levels. For this set of compounds, substituent effects on delta(53Cr) are better described with the pure BPW91 functional than with B3LYP, in contrast to most other transition-metal chemical shifts studied so far. For selected cases, 53Cr NMR line widths can be rationalized in terms of electric field gradients (EFGs) computed with the BPW91 functional, but in general other factors such as molecular correlation times appear to be dominating. 53Cr chemical shifts and EFGs are predicted for CrO3, Cr(C6H6)2, Cr(C6H6)CO3, and, with reduced reliability, for Cr2(mu2-O2CH)4.
Authors:
Michael Bühl
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Magnetic resonance in chemistry : MRC     Volume:  44     ISSN:  0749-1581     ISO Abbreviation:  Magn Reson Chem     Publication Date:  2006 Jul 
Date Detail:
Created Date:  2006-06-07     Completed Date:  2007-07-30     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9882600     Medline TA:  Magn Reson Chem     Country:  England    
Other Details:
Languages:  eng     Pagination:  661-8     Citation Subset:  -    
Copyright Information:
Copyright (c) 2006 John Wiley & Sons, Ltd.
Affiliation:
Max-Planck Institut für Kohlenforschung, Kaiser-Wilhelm Platz 1, D-45470 Mülheim an der Ruhr, Germany. buehl@mpi-muelheim.mpg.de
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