Počet záznamů: 1

Theoretical Insights into the Nature of Nickel-Carbon Dioxide Interactions in Ni(PH3)2(eta2-CO2)

  1. 1.
    0366966 - UCHP-M 2012 RIV US eng J - Článek v odborném periodiku
    Kegl, T. - Ponec, Robert - Kollar, L.
    Theoretical Insights into the Nature of Nickel-Carbon Dioxide Interactions in Ni(PH3)2(eta2-CO2).
    Journal of Physical Chemistry A. Roč. 115, č. 45 (2011), s. 12463-12473 ISSN 1089-5639
    Grant CEP: GA ČR GA203/09/0118
    Grant ostatní: HSRF(HU) OTKA NK 71906; HSRF(HU) OTKA-NKTH CK 78553; RTI(HU) SROP-4.2.2/08/1/2008-2011
    Výzkumný záměr: CEZ:AV0Z40720504
    Klíčová slova: carbon dioxide coordination to Ni * analysis of bonding interactions * density functional methods
    Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
    Impakt faktor: 2.946, rok: 2011

    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 pi-donation interaction the C-O sigma bond takes also part in the electron donation. Moreover, the back-donation is slightly influenced by the phosphorus atom adjacent to the non-coordinated 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.
    Trvalý link: http://hdl.handle.net/11104/0006653