Synthesis, X-ray crystal structure, and properties of antipyrinium perchlorates, hexakis(antipyrine)thulium- and hexakis(antipyrine)ytterbium perchlorates. Quantum-chemical studies of ligands protonation

• Published in: Russian journal of inorganic chemistry Vol. 59; no. 5; pp. 455 - 468
• Main Authors: Rukk, N. S., Albov, D. V., Shamsiev, R. S., Mudretsova, S. N., Osipov, R. A., Zamalyutin, V. V., Skryabina, A. Yu, Kravchenko, V. V.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.05.2014
• Subjects: Chemistry; Chemistry and Materials Science; Coordination Compounds; Crystal structure; Crystals; Inorganic Chemistry; Ligands; Mathematical analysis; Perchlorates; Protonation; Quantum chemistry; X-rays; Thulium; Antipyrine; Hexakis; Protonation Energy; Endo Effect
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023614050143

Protonation of the bioactive ligand-antipyrine (AP, 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) has been considered, the crystal packing specific features for the protonated antipyrine perchlorate compounds ([APH]ClO 4 · H 2 O ( 1 , 2) and [AP 2 H]ClO 4 ( 3 , 4 )), as well as the crystal structure particularities for [Tm(AP) 6 ](ClO 4 ) 3 ( 5 ) and [Yb(AP) 6 ](ClO 4 ) 3 ( 6 ) have been elucidated. The protonation ability—complex formation ability relationship has been revealed for a number of organic ligands. Quantum-chemical calculations (DFT) and comparison with the experimental data allowed aligning some organic ligands in a row according to their ability to be protonated and to be incorporated into the inner coordination sphere of the complex.