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Solvent effects on (15) N NMR coordination shifts.
MedLine Citation:
PMID:  23208996     Owner:  NLM     Status:  Publisher    
(15) N NMR chemical shift became a broadly utilized tool for characterization of complex structures and comparison of their properties. Despite the lack of systematic studies, the influence of solvent on the nitrogen coordination shift, Δ(15) N(coord) , was hitherto claimed to be negligible. Herein, we report the dramatic impact of the local environment and in particular that of the interplay between solvent and substituents on Δ(15) N(coord) . The comparative study of CDCl(3) and CD(3) CN solutions of silver(I)-bis(pyridine) and silver(I)-bis(pyridylethynyl)benzene complexes revealed the strong solvent dependence of their (15) N NMR chemical shift, with a solvent dependent variation of up to 40 ppm for one and the same complex. The primary influence of the effect of substituent and counter ion on the (15) N NMR chemical shifts is rationalized by corroborating Density-Functional Theory (nor discrete Fourier transform) calculations on the B3LYP/6-311 + G(2d,p)//B3LYP/6-31G(d) level. Cooperative effects have to be taken into account for a comprehensive description of the coordination shift and thus the structure of silver complexes in solution. Our results demonstrate that interpretation of Δ(15) N(coord) in terms of coordination strength must always consider the solvent and counter ion. The comparable magnitude of Δ(15) N(coord) for reported transition metal complexes makes the principal findings most likely general for a broad scale of complexes of nitrogen donor ligands, which are in frequent use in modern organometallic chemistry. Copyright © 2012 John Wiley & Sons, Ltd.
Roland Kleinmaier; Sven Arenz; Alavi Karim; Anna-Carin C Carlsson; Máté Erdélyi
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-12-4
Journal Detail:
Title:  Magnetic resonance in chemistry : MRC     Volume:  -     ISSN:  1097-458X     ISO Abbreviation:  Magn Reson Chem     Publication Date:  2012 Dec 
Date Detail:
Created Date:  2012-12-4     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9882600     Medline TA:  Magn Reson Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 John Wiley & Sons, Ltd.
Department of Chemistry and Molecular Biology and the Swedish NMR Centre, University of Gothenburg, Kemivägen 10, 412 96, Göteborg, Sweden.
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