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Synthesis, Structural and Spectroscopic Characterization of Cr III , Fe III , Co III , Ni II and Cu II Complexes with an Asymmetric 1,3,4‐Thiadiazole Ligand
Author(s) -
Deckert Christoph,
Bittner Denis,
Carrella Luca M.,
Schollmeyer Dieter,
Rentschler Eva
Publication year - 2016
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.201501400
Subject(s) - chemistry , crystallography , ligand (biochemistry) , electron paramagnetic resonance , magnetic susceptibility , tetramer , copper , molecule , supramolecular chemistry , coordination sphere , crystal structure , metal , stereochemistry , biochemistry , physics , receptor , enzyme , organic chemistry , nuclear magnetic resonance
The reaction of the new asymmetric 1,3,4‐thiadiazole‐based ligand 2‐[(5‐ethylthio‐1,3,4‐thiadiazol‐2‐yl)hydrazonomethyl]phenol (H 1 ETHP) with various third‐row transition metal salts resulted in the formation of six new mononuclear complexes [Cr(ETHP) 2 ]ClO 4 ( 1 ), [Fe(ETHP) 2 ][FeCl 4 ] ( 2 ), [Co(ETHP)(ETHP –H )] ( 3 ), [Ni(ETHP)(H 1 ETHP)]Cl ( 4 ), [Ni(ETHP)(H 1 ETHP)](ClO 4 ) ( 5 ), [Ni(ETHP)(H 1 ETHP)]Br ( 6 ), and one tetranuclear complex [Cu 2 Cl 3 (ETHP)(H 1 ETHP)] 2 ( 7 ). H 1 ETHP and all complexes have been analyzed by single crystal X‐ray diffraction. Structural analysis of 1 – 6 reveals complexes of the [ML 2 ] n + ‐type ( n = 0,1), in which the mono anionic ligand ETHP coordinates in a tridentate NNO fashion via its imine, thiadiazole and phenolate functional groups. Complex 7 has also been investigated by variable‐temperature magnetic susceptibility measurements and shows weak antiferromagnetic exchange interactions between the copper centers. The g values for the copper ions in the tetramer were obtained by EPR spectroscopy. All compounds were found to display an extended hydrogen bond network via their N–H or O–H ligand functional groups towards the corresponding counterions, solvent molecules or neighboring complex cations. The connectivity of the complexes results in the formation of supramolecular chains or, in the case of 4 , a 3D‐network including large solvent accessible cavities.