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Description of the metal–ligand bonding in f‐element complexes: A DFT study including scalar relativistic effects
Author(s) -
Vetere Valentina,
Maldivi Pascale,
Adamo Carlo
Publication year - 2002
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.10448
Subject(s) - chemistry , relativistic quantum chemistry , iodide , halogen , ligand (biochemistry) , density functional theory , metal , scalar (mathematics) , acceptor , computational chemistry , halide , halogen bond , hamiltonian (control theory) , crystallography , inorganic chemistry , atomic physics , physics , quantum mechanics , organic chemistry , mathematical optimization , biochemistry , alkyl , receptor , geometry , mathematics
A comparative density functional study on metal–ligand (M–L) interaction has been performed on X 3 –M–L (X = F, I; M = U, La, Nd: L = NH 3 , NCCH 3 , CO) and X 3 –M–(CO) 2 species including scalar relativistic effects by means of the zero‐order regular approximation (ZORA) hamiltonian. The role of the halogen atoms in modeling the M–L interactions is discussed for π‐acceptor ligands CO and NCCH 3 and for the σ‐donor NH 3 . The fluoride counterions, compared with previous calculations on the iodide complexes, stabilize more tedraedral structure with longer M–L distances. Finally, the addition of a second ligand to the previous species has permitted a more complete discussion on the backbonding effects on the uranium complexes. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003