Substituent effects on 61Ni NMR chemical shifts

Michael Bühl; Dietmund Peters; Rainer Herges

doi:10.1039/B902308A

Substituent effects on ⁶¹Ni NMR chemical shifts†

Michael Bühl,‡*^a Dietmund Peters^b and Rainer Herges^b

* Corresponding authors

^a Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, Germany
E-mail: buehl@st-andrews.ac.uk
Fax: +(44)(0)1334 463808

^b Otto-Diels-Institut für Organische Chemie, Universität Kiel
E-mail: rherges@oc.uni-kiel.de

Abstract

⁶¹Ni 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 δ(⁶¹Ni) 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 ⁶¹Ni 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 ⁶¹Ni NMR line for the all-cis-cdt complex, rationalizing the apparent failure to record the NMR spectrum experimentally.

This article is part of the themed collection: The synergy between theory and experiment

Article information

https://doi.org/10.1039/B902308A

Article type

Paper

Submitted

04 Feb 2009

Accepted

25 Mar 2009

First published

28 Apr 2009

Download Citation

Dalton Trans., 2009, 6037-6044

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Substituent effects on ⁶¹Ni NMR chemical shifts

M. Bühl, D. Peters and R. Herges, Dalton Trans., 2009, 6037 DOI: 10.1039/B902308A

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