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Formation of Mono‐, Di‐ and Trinuclear Species in the Self‐Assembly of Bis(pyrazolyl)(pyridin‐3‐yl)methane Ligands and Metals with Different Coordination Geometries
Author(s) -
Durá Gema,
Carrión M. Carmen,
Jalón Félix A.,
Manzano Blanca R.,
Rodríguez Ana M.
Publication year - 2015
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.201501077
Subject(s) - chemistry , pyridine , palladium , substituent , medicinal chemistry , supramolecular chemistry , metal , nickel , chirality (physics) , tetracoordinate , ring (chemistry) , stereochemistry , transition metal , methane , crystal structure , catalysis , crystallography , organic chemistry , nambu–jona lasinio model , chiral symmetry breaking , physics , computer graphics (images) , quantum mechanics , computer science , planar , quark
The self‐assembly of ligands bis(pyrazol‐1‐yl)(pyridin‐3‐yl)methane (bpzm3py, L1 ) and bis(3,5‐dimethylpyrazol‐1‐yl)(pyridin‐3‐yl)methane (bpz*m3py, L2 ), with metals of different geometries has been investigated. The use of [PdCl 2 (PhCN) 2 ] led to the formation of trinuclear species of the type [PdCl 2 (μ‐L)PdCl 2 (μ‐L)PdCl 2 ] with two types of palladium centre. The use of Ni(NO 3 ) 2 led to the formation of cyclic dimers [Ni(μ‐L)(NO 3 ) 2 ] 2 , in which the ligands L adopt a head‐to‐tail disposition, whereas the reaction with CoCl 2 led to mononuclear species [CoCl 2 (L)] with an uncoordinated pyridine ring. The reaction with silver salts gave, in all cases, cyclic dimers with tetracoordinate metal ions. In the cases of AgClO 4 and AgCF 3 SO 3 , the products were [Ag(μ‐L)(X)] 2 with the anions coordinated to the metal ions. In the case of AgBF 4 , the anion remained uncoordinated and the resulting species, [Ag(μ‐L)(S) 2 ] 2 (BF 4 ) 2 , contained coordinated crystallisation solvents (S = MeOH, acetone). The asymmetry in the ligands created by the 3‐substituent in the pyridine ring led to the generation of chirality in the case of the nickel and silver cyclic dimers. The supramolecular structures were analysed and a comparison was made with the structures of complexes that contain the related ligands bis(pyrazol‐1‐yl)(pyridin‐4‐yl)methane and bis(3,5‐dimethylpyrazol‐1‐yl)(pyridin‐4‐yl)methane. A “pyrazolyl embrace” was observed in a silver complex with the non‐methylated ligand L1 .