Substituent effects on Ni-61 NMR chemical shifts

Michael Buehl; Dietmund Peters; Rainer Herges

doi:10.1039/b902308a

Substituent effects on Ni-61 NMR chemical shifts

Michael Buehl, Dietmund Peters, Rainer Herges

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	6037-6044
Number of pages	8
Journal	Dalton Transactions
Issue number	30
Early online date	28 Apr 2009
DOIs	https://doi.org/10.1039/b902308a
Publication status	Published - 2009

Keywords

Density-functional computation
Transition-metal-complexes
Correlation-energy
Electron-diffraction
Aromaticity probe
NMR
Spectroscopy
Exchange
Tris(ethylene)nickel(0)
Approximation

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10.1039/b902308a

Open Access version in Research@StAndrews:FullText
This is the revised, accepted version of this article following peer review. Published version (c)2009 The Royal Society of Chemistry
Accepted author manuscript, 663 KB

Cite this

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title = "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.",

keywords = "Density-functional computation, Transition-metal-complexes, Correlation-energy, Electron-diffraction, Aromaticity probe, NMR, Spectroscopy, Exchange, Tris(ethylene)nickel(0), Approximation",

author = "Michael Buehl and Dietmund Peters and Rainer Herges",

note = "{"}This paper is published as part of a Dalton Transactions themed issue on: The Synergy between Theory and Experiment{"} ",

year = "2009",

doi = "10.1039/b902308a",

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journal = "Dalton Transactions",

issn = "1477-9226",

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TY - JOUR

T1 - Substituent effects on Ni-61 NMR chemical shifts

AU - Buehl, Michael

AU - Peters, Dietmund

AU - Herges, Rainer

N1 - "This paper is published as part of a Dalton Transactions themed issue on: The Synergy between Theory and Experiment"

PY - 2009

Y1 - 2009

N2 - 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.

AB - 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.

KW - Density-functional computation

KW - Transition-metal-complexes

KW - Correlation-energy

KW - Electron-diffraction

KW - Aromaticity probe

KW - NMR

KW - Spectroscopy

KW - Exchange

KW - Tris(ethylene)nickel(0)

KW - Approximation

U2 - 10.1039/b902308a

DO - 10.1039/b902308a

M3 - Article

SN - 1477-9226

SP - 6037

EP - 6044

JO - Dalton Transactions

JF - Dalton Transactions

IS - 30

ER -

Substituent effects on Ni-61 NMR chemical shifts

Abstract

Keywords

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