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New template reactions of salicylaldehyde S-methyl-isothiosemicarbazone with 2-formylpyridine promoted by Ni(II) or Cu(II) metal ions
Authors:Mihail D Revenco  Oleg V Palamarciuc  Paulina N Bourosh  Maria Gdaniec  Rodolphe Clérac
Institution:a State University of Moldova, Mateevici 60, Chisinau MD-2009, Republic of Moldova
b CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 Avenue du Dr. Albert Schweitzer, Pessac F-33600, France
c Université de Bordeaux, UPR 8641, Pessac F-33600, France
d Institute of Applied Physics, Academy of Sciences of Moldova, Academiei 5, Chisinau 2028, Republic of Moldova
e Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01 224 Warsaw, Poland
f Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
Abstract:The template reaction between salicylaldehyde S-methyl-isothiosemicarbazone and 2-formylpyridine in presence of nickel(II) or copper(II) salts yields two new coordination compounds with general formula NiL1]2(1) and CuL2]2(2) (L1 = the dianionic (N1-salicylidene)(N4-(hydroxy(pyridin-2-yl)methyl) S-methyl-isothiosemicarbazide) ligand and L2 = the doubly deprotonated (N1-salicylidene)(N4-(picolinoyl) S-methyl-isothiosemicarbazide) ligand). In the complex 1, the formed L1 ligand appears as result of an addition reaction of the precursors, while for 2 a redox mechanism is implicated in the formation of L2. Despite the fact that the initial organic precursors are the same, the resulting ligands obtained in the template reaction are different. In 1, the Ni(II) metal ion adopts a square-planar geometry and the NiL1] units are forming dimerized chains through weak Ni···Ni interactions (3.336 and 3.632 Å). In 2, the Cu(II) metal ions adopt a square-pyramidal geometry and form dinuclear species through weak Cu···O (phenoxo) interactions. The magnetic susceptibility measurements of the complexes reveal the diamagnetic nature of 1 as expected for a square planar Ni(II) complex and a paramagnetic behavior for 2 with weak intra-dimer antiferromagnetic interaction (J/kB = −2.1(1) K).
Keywords:Template reaction  Isothiosemicarbazide ligand  X-ray crystal structure  Nickel(II) complex  Copper(II) complex  Magnetic properties
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