Theoretical insights into the nature of nickel-carbon dioxide interactions in Ni(PH 3) 22-CO 2)

T. Kégl, Robert Ponec, L. Kollár

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

DFT calculations were carried out for the Ni(0) complex Ni(PH 3) 22-CO 2), which is a model compound for the well-known Ni(0) carbon dioxide complexes containing various tertiary phosphane ligands. The electronic structure of the complex was elucidated using domain-averaged Fermi hole (DAFH), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), charge decomposition analysis (CDA), and natural bond orbital (NBO) methods. The carbon dioxide ligand in the complex reveals an unexpected coordination behavior. Apart from the expected π-donation interaction, the C-O σ bond takes also part in the electron donation. Moreover, the back-donation is slightly influenced by the phosphorus atom adjacent to the noncoordinated O of carbon dioxide as it transfers electron density directly to carbon. This unconventional way of back-donation may also explain the bent character of the Ni-C bond path. Due to excess kinetic energy density, no bond critical point was found between the coordinating oxygen and the nickel center. A strong relationship has been found between the DAFH and the NBO methods, which can provide additional information for the interpretation of DAFH eigenvectors.

Original languageEnglish
Pages (from-to)12463-12473
Number of pages11
JournalJournal of Physical Chemistry A
Volume115
Issue number45
DOIs
Publication statusPublished - Nov 17 2011

Fingerprint

Carbon Monoxide
Nickel
Carbon Dioxide
carbon dioxide
phosphine
nickel
Ligands
orbitals
Atoms
ligands
Electrons
Quantum theory
interactions
Discrete Fourier transforms
Eigenvalues and eigenfunctions
quantum theory
Kinetic energy
Phosphorus
Electronic structure
Carrier concentration

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical insights into the nature of nickel-carbon dioxide interactions in Ni(PH 3) 22-CO 2). / Kégl, T.; Ponec, Robert; Kollár, L.

In: Journal of Physical Chemistry A, Vol. 115, No. 45, 17.11.2011, p. 12463-12473.

Research output: Contribution to journalArticle

@article{7866b4ef19f6471186df9cf3e38975c1,
title = "Theoretical insights into the nature of nickel-carbon dioxide interactions in Ni(PH 3) 2(η 2-CO 2)",
abstract = "DFT calculations were carried out for the Ni(0) complex Ni(PH 3) 2(η 2-CO 2), which is a model compound for the well-known Ni(0) carbon dioxide complexes containing various tertiary phosphane ligands. The electronic structure of the complex was elucidated using domain-averaged Fermi hole (DAFH), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), charge decomposition analysis (CDA), and natural bond orbital (NBO) methods. The carbon dioxide ligand in the complex reveals an unexpected coordination behavior. Apart from the expected π-donation interaction, the C-O σ bond takes also part in the electron donation. Moreover, the back-donation is slightly influenced by the phosphorus atom adjacent to the noncoordinated O of carbon dioxide as it transfers electron density directly to carbon. This unconventional way of back-donation may also explain the bent character of the Ni-C bond path. Due to excess kinetic energy density, no bond critical point was found between the coordinating oxygen and the nickel center. A strong relationship has been found between the DAFH and the NBO methods, which can provide additional information for the interpretation of DAFH eigenvectors.",
author = "T. K{\'e}gl and Robert Ponec and L. Koll{\'a}r",
year = "2011",
month = "11",
day = "17",
doi = "10.1021/jp201140h",
language = "English",
volume = "115",
pages = "12463--12473",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "45",

}

TY - JOUR

T1 - Theoretical insights into the nature of nickel-carbon dioxide interactions in Ni(PH 3) 2(η 2-CO 2)

AU - Kégl, T.

AU - Ponec, Robert

AU - Kollár, L.

PY - 2011/11/17

Y1 - 2011/11/17

N2 - DFT calculations were carried out for the Ni(0) complex Ni(PH 3) 2(η 2-CO 2), which is a model compound for the well-known Ni(0) carbon dioxide complexes containing various tertiary phosphane ligands. The electronic structure of the complex was elucidated using domain-averaged Fermi hole (DAFH), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), charge decomposition analysis (CDA), and natural bond orbital (NBO) methods. The carbon dioxide ligand in the complex reveals an unexpected coordination behavior. Apart from the expected π-donation interaction, the C-O σ bond takes also part in the electron donation. Moreover, the back-donation is slightly influenced by the phosphorus atom adjacent to the noncoordinated O of carbon dioxide as it transfers electron density directly to carbon. This unconventional way of back-donation may also explain the bent character of the Ni-C bond path. Due to excess kinetic energy density, no bond critical point was found between the coordinating oxygen and the nickel center. A strong relationship has been found between the DAFH and the NBO methods, which can provide additional information for the interpretation of DAFH eigenvectors.

AB - DFT calculations were carried out for the Ni(0) complex Ni(PH 3) 2(η 2-CO 2), which is a model compound for the well-known Ni(0) carbon dioxide complexes containing various tertiary phosphane ligands. The electronic structure of the complex was elucidated using domain-averaged Fermi hole (DAFH), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), charge decomposition analysis (CDA), and natural bond orbital (NBO) methods. The carbon dioxide ligand in the complex reveals an unexpected coordination behavior. Apart from the expected π-donation interaction, the C-O σ bond takes also part in the electron donation. Moreover, the back-donation is slightly influenced by the phosphorus atom adjacent to the noncoordinated O of carbon dioxide as it transfers electron density directly to carbon. This unconventional way of back-donation may also explain the bent character of the Ni-C bond path. Due to excess kinetic energy density, no bond critical point was found between the coordinating oxygen and the nickel center. A strong relationship has been found between the DAFH and the NBO methods, which can provide additional information for the interpretation of DAFH eigenvectors.

UR - http://www.scopus.com/inward/record.url?scp=80855150868&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80855150868&partnerID=8YFLogxK

U2 - 10.1021/jp201140h

DO - 10.1021/jp201140h

M3 - Article

C2 - 21449600

AN - SCOPUS:80855150868

VL - 115

SP - 12463

EP - 12473

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 45

ER -