Substituent effects on Ni-61 NMR chemical shifts
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.
Citation
Buehl , M , Peters , D & Herges , R 2009 , ' Substituent effects on Ni-61 NMR chemical shifts ' , Dalton Transactions , no. 30 , pp. 6037-6044 . https://doi.org/10.1039/b902308a
Publication
Dalton Transactions
Status
Peer reviewed
ISSN
1477-9226Type
Journal article
Rights
This is the revised, accepted version of this article following peer review. Published version (c)2009 The Royal Society of Chemistry
Description
"This paper is published as part of a Dalton Transactions themed issue on: The Synergy between Theory and Experiment"Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.