On the Electronic Structure of mer,trans-[RuCl3(1H-indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

0424454 - ÚCHP 2014 RIV DE eng J - Článek v odborném periodiku
Bučinský, L. - Buchel, G.E. - Ponec, Robert - Rapta, P. - Breza, M. - Kožíšek, J. - Gall, M. - Biskupič, S. - Fronc, M. - Schiessl, K. - Cuzan, O. - Prodius, D. - Turta, C. - Shova, S. - Zajac, D.A. - Arion, V.B.
On the Electronic Structure of mer,trans-[RuCl3(1H-indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study.
European Journal of Inorganic Chemistry. Roč. 14, MAY (2013), s. 2505-2519. ISSN 1434-1948. E-ISSN 1099-0682
Grant CEP: GA ČR GA203/09/0118
Grant ostatní: GA SK(SK) 1/0679/11; GA SK(SK) 1/0289/12; GA SK(SK) 1/0327/12; AAIM(AT) SK-03; ASF(AT) I 374-N19
Institucionální podpora: RVO:67985858
Klíčová slova: ruthenium * electronic structure * antitumor agents
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.965, rok: 2013

The study reported herein focused on the electronic structure of the {Ru(NO)}6 fragment and characterization of the oxidation state of ruthenium in mer,trans-[RuCl3(Hind)2(NO)] (1; Hind = 1H-indazole) resulting from the reaction of mer,trans-[RuCl3(H2O)(Hind)2] (2) with NO in acetone or solid-state Anderson rearrangement of (H2ind)2[RuCl5(NO)] at 180 degrees C. The results of X-ray diffraction, 1H, 13C, and 15N NMR, EPR, IR, and UV/Vis spectroscopy, cyclic voltammetry, magnetic susceptibility, and XANES/EXAFS as well as theoretical data have been critically analyzed. The localized orbitals, domain-averaged Fermi holes, frontier orbitals, Mulliken population, and quantum theory of atoms-in-molecules (QTAIM) analyses are presented. In addition, mer,trans-[RuIIICl3(H2O)(Hind)2] (2) and trans-[RuIICl2(Hind)4] (3) were experimentally and theoretically investigated as reference compounds. A complete active space SCF calculation was performed to estimate the extent of antiferromagnetic spinspin coupling in 1. We found that the closed-shell structure {RuIII(NO)0}6 fits better to the physical/spectroscopic properties of 1, although {RuII(NO)+}6 is formally still suitable for describing the oxidation state of Ru in this entity.
Trvalý link: http://hdl.handle.net/11104/0230526