Nature of the Metal-Ligand Interactions in Complexes M(PH3)(2)(eta(2)-L) (M=Ni, Pd, Pt; L=CO2, COS, CS2): A Theoretical Study

作者：Palinkas Noemi; Kollar Laszlo; Kegl Tamas^*

来源：ChemistrySelect, 2017, 2(20): 5740-5750.

DOI：10.1002/slct.201700897

• Carbon dioxide
• Carbon disulfide
• Carbonyl sulfide
• Electronic structure calculations

DFT calculations have been carried out for complexes M(0)(PH3)(2)(eta(2)-(CEE2)-E-1), where M=Ni, Pd, Pt, and E-1, E-2=O, S. The electronic structure of the complexes have been elucidated using various methods, such as quantum theory of atoms in molecules (QTAIM), electron localization ELF), domain-averaged Fermi hole (DAFH), and energy decomposition analysis combined with the natural orbital of chemical valence (EDA-NOCV). In the carbonyl sulfide complexes the eta(2)-(S,C) coordination is clearly preferred over eta(2)-(O,C) which might be attributed to the harder character of oxygen reflected in excess kinetic energy density preventing the formation of bond paths in the vicinity of the metal center and the coordinating oxygen. The nature of the interaction between the metal containing fragment and the ligand is closed-shell donor-acceptor, rather than 'classical' (shared-shell) covalent type which is dominated by the back-donating interactions.

• 出版日期2017-7-11