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

0366966 - ÚCHP 2012 RIV US eng J - Journal Article
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. E-ISSN 1520-5215
R&D Projects: GA ČR GA203/09/0118
Grant - others:HSRF(HU) OTKA NK 71906; HSRF(HU) OTKA-NKTH CK 78553; RTI(HU) SROP-4.2.2/08/1/2008-2011
Institutional research plan: CEZ:AV0Z40720504
Keywords : carbon dioxide coordination to Ni * analysis of bonding interactions * density functional methods
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.946, year: 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.
Permanent Link: http://hdl.handle.net/11104/0006653