1. Substituent effects on Ni-61 NMR chemical shifts
- Author
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Dietmund Peters, Michael Bühl, Rainer Herges, University of St Andrews. School of Chemistry, and University of St Andrews. EaSTCHEM
- Subjects
Electron-diffraction ,Substituent ,Tris(ethylene)nickel(0) ,Faculty of Mathematics and Natural Sciences ,Density-functional computation ,Transition-metal-complexes ,Aromaticity probe ,Inorganic Chemistry ,chemistry.chemical_compound ,Correlation-energy ,Computational chemistry ,QD ,Spectroscopy ,Approximation ,ddc:5 ,chemical shifts ,Chemical shift ,article ,Exchange ,Nuclear magnetic resonance spectroscopy ,QD Chemistry ,NMR ,Hybrid functional ,chemistry ,ddc:540 ,Physical chemistry ,Cyclododecatriene ,Mathematisch-Naturwissenschaftliche Fakultät ,Electric field gradient ,Cyclooctadiene - Abstract
"This paper is published as part of a Dalton Transactions themed issue on: The Synergy between Theory and Experiment" 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. Postprint
- Published
- 2009