New template reactions of salicylaldehyde S-methyl-isothiosemicarbazone with 2-formylpyridine promoted by Ni(II) or Cu(II) metal ions

• Published in: Inorganica Chimica Acta 2011-03, Vol.368 (1), p.157-164
• Main Authors: Revenco, Mihail D., Palamarciuc, Oleg V., Bourosh, Paulina N., Lipkowski, Janusz, Gdaniec, Maria, Simonov, Yurii A., Clérac, Rodolphe
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Copper(II) complex; Inorganic chemistry; Isothiosemicarbazide ligand; Magnetic properties; Nickel(II) complex; Template reaction; X-ray crystal structure
• ISSN: 0020-1693; 1873-3255; 0020-1693
• DOI: 10.1016/j.ica.2010.12.068

The template reaction between salicylaldehyde S-methyl-isothiosemicarbazone and 2-formylpyridine in presence of Ni(II) or Cu(II) yields two new complexes. The formed ligands appears as result of an addition reaction of the precursors with Ni(II), while a redox mechanism is implicated in the formation of the ligand in presence of Cu(II). [Display omitted] ► New Ni(II) complex of salicylaldehyde S-CH3-isothiosemicarbazone derivative. ► New Cu(II) complex of salicylaldehyde S-CH3-isothiosemicarbazone derivative. ► Template reactions of salicylaldehyde S-CH3-isothiosemicarbazone and 2-formylpyridine. ► New tetradentate ligands derivated from S-alkylated-isothiosemicarbazide. 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 3.632Å). 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).