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A Theoretical Study on Pd II Complexes Containing Hemilabile Pyrazole‐Derived Ligands
Author(s) -
Rimola Albert,
Sodupe Mariona,
Ros Josep,
Pons Josefina
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500794
Subject(s) - chemistry , pyrazole , tetracoordinate , substituent , ring (chemistry) , atom (system on chip) , stereochemistry , medicinal chemistry , density functional theory , carbon atom , ligand (biochemistry) , crystallography , computational chemistry , organic chemistry , biochemistry , computer graphics (images) , receptor , computer science , planar , embedded system
The properties of Pd II complexes containing hemilabile pyrazole‐derived ligands (L) of the form BPz‐(CH 2 ) x A(CH 2 ) y A(CH 2 ) x ‐PzB, with A being a donor atom and B a substituent group at the pyrazole ring, have been investigated through quantum‐chemical calculations. The geometries of the [PdLCl 2 ] and [PdL] 2+ complexes have been optimized and the reaction free energy of [PdLCl 2 ] → [PdL] 2+ + 2 Cl – computed for 32 different ligands, using the hybrid B3LYP density functional method. The formation of the tetracoordinate [PdL] 2+ complexes is more favorable for the longer (eight‐ and nine‐membered) chains than for the shorter (six‐ and seven‐membered) ones. Moreover, results show the nature of the donor atom A influences significantly the formation of [PdL] 2+ , the process becoming more favorable according to the order PH > NH > S > O. Finally, electron‐donor substituents at the pyrazole ring enhance the formation of [PdL] 2+ , whereas electron‐acceptor groups hinder the process. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)