DFT investigations of the structure and bonding between transition metals and olefins

Bögel, Horst; Tobisch, Sven; Nowak, Thomas

doi:10.1002/(sici)1097-461x(1998)69:3<387::aid-qua16>3.3.co;2-9

Cited by 5 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Ni 2þ (C 2 H 4 ) is predicted to be a C s structure (Alexander & Dines, 2004). For Ni 2þ -butadiene complexes, the h 4 -structure, in which the metal interacts with the four carbon atoms was the only local minimum found, for both the cis and the trans isomers, the former being 22 kJ/mol more stable (Bögel, Tobisch, & Nowak, 1998) than the latter.…”

Section: Ni 2þ -Complexesmentioning

confidence: 97%

“…Theoretical studies on Ni 2þ complexes with ethene (Alexander & Dines, 2004) and butadiene (Bögel, Tobisch, & Nowak, 1998) concluded that the high positive charge on the metal reduces significantly backdonation interactions from the metal to the neutral base, and this diminishes also the donation from the carbon atoms since its positive charge is not compensated through the backdonation. Consistently, the geometry distortions in both ethane and butadiene are smaller in Ni 2þ than in Ni 0 complexes.…”

Section: Ni 2þ -Complexesmentioning

confidence: 99%

See 1 more Smart Citation

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Mó

Yáñez

Salpin

et al. 2007

Mass Spectrometry Reviews

View full text Add to dashboard Cite

In this review, we present a general overview on the studies carried out on Ni(+-)- and Ni(2+)-containing systems in the gas phase since 1996. We have focused our attention in the determination of binding energies in parallel with an analysis of the structure and bonding of the complexes formed by the interaction of Ni(+) with one ligand, or in clusters where this metal ion binds several identical or different ligands. Solvation of Ni(2+) by different ligands is also discussed, together with the theoretical information available of doubly charged Ni-containing species. The final section of this review is devoted to an analysis of the gas-phase uni- and bimolecular reactivity of Ni(+) and Ni(2+) complexes.

show abstract

Section: Ni 2þ -Complexesmentioning

confidence: 97%

Section: Ni 2þ -Complexesmentioning

confidence: 99%

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Mó

Yáñez

Salpin

et al. 2007

Mass Spectrometry Reviews

View full text Add to dashboard Cite

show abstract

“…Hence, it is observed that though there is a change in the relative stabilities, the ground-state geometry of the Ni(C 4 H 6 ), obtained in our calculations, has remained unaffected by the choice of basis set. Therefore, on the basis of this observation, we conclude that the disagreement between our calculated results and the previous calculations 6 can be attributed to the choice of the energy functionals and to a lesser degree on the choice of different basis sets. The structural parameters of the η 4 -trans and η 2 -trans complexes obtained from our calculations are in good agreement with the previous calculations.…”

Section: Resultsmentioning

confidence: 60%

“…Theoretical calculations on Ni-butadiene complex are limited. A semiempirical calculation on Ni(C 4 H 6 ) complex, 5 and a DFTbased calculation 6 on Ni interaction with ethylene, and butadienes have been reported previously. In the DFT-based investigation, 6 only Ni(C 4 H 6 ) and Ni 2+ (C 4 H 6 ) complexes were taken into account.…”

Section: Introductionmentioning

confidence: 99%

“…A semiempirical calculation on Ni(C 4 H 6 ) complex, 5 and a DFTbased calculation 6 on Ni interaction with ethylene, and butadienes have been reported previously. In the DFT-based investigation, 6 only Ni(C 4 H 6 ) and Ni 2+ (C 4 H 6 ) complexes were taken into account. To our knowledge, no systematic calculations exist on larger complexes of Ni(C 4 H 6 ), in which the equilibrium geometries and the nature of chemical bonds between the metal atom and butadiene are analyzed.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Binding of Butadiene Molecules Mediated by Ni Atom and Ni⁺ Ion

et al. 2004

View full text Add to dashboard Cite

Theoretical ab initio calculations based on density functional theory including gradient corrections have been performed to study the binding of cis-and trans-1,3-butadiene molecules mediated by Ni atom and Ni + ion. The geometries and dissociation energies are calculated to study the importance of Ni in the binding process. In the equilibrium geometry of Ni(butadiene) complex, the metal atom is found to position itself above the butadiene molecule and is bonded to all the carbon atoms in both the isomers of butadiene. The neutral and cationic Ni(butadiene) 2 complexes prefer three-dimensional structures with the Ni atom/ion sandwiched between the two butadiene molecules. This leads to the embedding of Ni atom or Ni + ion between the butadiene molecules during the binding process. The ground-state geometries of these complexes are stable against dissociation into smaller complexes, with Ni + (butadiene) complex being the most stable one among all the complexes studied.

show abstract

Ab Initio Calculations of the Structures and Vibrational Spectra of Ethene Complexes

Alexander

Dines

2003

J. Phys. Chem. A

View full text Add to dashboard Cite

To facilitate an objective comparison of the efficacy of the simulation of structural parameters and vibrational spectra of transition-metal complexes of commonly used ab initio methods, the geometries of the ethene complexes of Ni(0) and Ni(II) have been optimized using both ab initio and density functional theory (DFT) calculations and a wide variety of basis sets. The harmonic vibrational spectra of [Ni(C2H4)] and [Ni(C2H4)]2+ have been evaluated from the optimized geometries at Hartree−Fock, post-Hartree−Fock Møller−Plesset perturbation theory, MP2, and a range of DFT functionals. Upon comparison with experimental data, it has been found that hybrid DFT functionals, specifically B3-LYP, afford the most accurate fit to the experimental data. This is especially the case when using the all-electron DZVP basis set, which provides highly accurate results. The use of the effective core potential LanL2DZ basis set has been found to achieve a comparable level of accuracy to the DZVP basis set, at a fraction of the computational efficiency. Extension of these calculations to ethene complexes of other transition metals has revealed trends in their structures and vibrational spectra.

show abstract

DFT investigations of the structure and bonding between transition metals and olefins

Cited by 5 publications

References 0 publications

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Binding of Butadiene Molecules Mediated by Ni Atom and Ni⁺ Ion

Ab Initio Calculations of the Structures and Vibrational Spectra of Ethene Complexes

Contact Info

Product

Resources

About

DFT investigations of the structure and bonding between transition metals and olefins

Cited by 5 publications

References 0 publications

Thermochemistry, bonding, and reactivity of Ni+and Ni2+in the gas phase

Thermochemistry, bonding, and reactivity of Ni+and Ni2+in the gas phase

Binding of Butadiene Molecules Mediated by Ni Atom and Ni+ Ion

Ab Initio Calculations of the Structures and Vibrational Spectra of Ethene Complexes

Contact Info

Product

Resources

About

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Thermochemistry, bonding, and reactivity of Ni⁺and Ni²⁺in the gas phase

Binding of Butadiene Molecules Mediated by Ni Atom and Ni⁺ Ion