Research@StAndrews
 
The University of St Andrews

Research@StAndrews:FullText >
University of St Andrews Research >
University of St Andrews Research >
University of St Andrews Research >

Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/1674
This item has been viewed 36 times in the last year. View Statistics

Files in This Item:

File Description SizeFormat
pubNiNMR.pdf662.79 kBAdobe PDFView/Open
Title: Substituent effects on Ni-61 NMR chemical shifts
Authors: Buehl, Michael
Peters, Dietmund
Herges, Rainer
Keywords: Density-functional computation
Transition-metal-complexes
Correlation-energy
Electron-diffraction
Aromaticity probe
NMR
Spectroscopy
Exchange
Tris(ethylene)nickel(0)
Approximation
QD Chemistry
Issue Date: 2009
Citation: Buehl , M , Peters , D & Herges , R 2009 , ' Substituent effects on Ni-61 NMR chemical shifts ' Dalton Transactions , no. 30 , pp. 6037-6044 .
Abstract: Ni-61 chemical shifts of Ni(all-trans-cdt) L (cdt = cyclododecatriene, L = none, CO, PMe3), Ni(CO)(4), Ni(C2H4)(2)(PMe3), Ni(cod)(2) (cod = cyclooctadiene) and Ni(PX3)(4) (X = Me, F, Cl) are computed at the GIAO (gauge-including atomic orbitals), BPW91, B3LYP and BHandHLYP levels, using BP86-optimised geometries and an indirect referencing scheme. For this set of compounds, substituent effects on delta(Ni-61) are better described with hybrid functionals than with the pure BPW91 functional. On going from Ni(all-trans-cdt) to Ni(all-cis-cdt) the computations predict substantial shielding of the Ni-61 nucleus by nearly 700 ppm, as well as a sharp increase of the electric field gradient at this position. The latter result is predicted to afford an undetectably broad Ni-61 NMR line for the all-cis-cdt complex, rationalizing the apparent failure to record the NMR spectrum experimentally.
Version: Postprint
Description: "This paper is published as part of a Dalton Transactions themed issue on: The Synergy between Theory and Experiment"
Status: Peer reviewed
URI: http://hdl.handle.net/10023/1674
DOI: http://dx.doi.org/10.1039/b902308a
ISSN: 1477-9226
Type: Journal article
Rights: This is the revised, accepted version of this article following peer review. Published version (c)2009 The Royal Society of Chemistry
Appears in Collections:University of St Andrews Research
Chemistry Research



This item is protected by original copyright

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

 

DSpace Software Copyright © 2002-2012  Duraspace - Feedback
For help contact: Digital-Repository@st-andrews.ac.uk | Copyright for this page belongs to St Andrews University Library | Terms and Conditions (Cookies)