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Nature of the Metal‐Ligand Interactions in Complexes M(PH 3 ) 2 ( η 2 ‐L) (M=Ni, Pd, Pt; L=CO 2 , COS, CS 2 ): A Theoretical Study
Author(s) -
Pálinkás Noémi,
Kollár László,
Kégl Tamás
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201700897
Subject(s) - chemistry , ligand (biochemistry) , valence (chemistry) , atomic orbital , crystallography , natural bond orbital , atoms in molecules , covalent bond , density functional theory , metal , electron localization function , molecule , electronic structure , acceptor , valence electron , computational chemistry , electron , physics , quantum mechanics , biochemistry , receptor , organic chemistry
DFT calculations have been carried out for complexes M(0)(PH 3 ) 2 ( η 2 ‐CE 1 E 2 ), 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 function (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 η 2 ‐(S,C) coordination is clearly preferred over η 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.