Projekte

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

Autor(en)
Lukas Bucinsky, Gabriel Büchel, Robert Ponec, Peter Rapta, Martin Breza, Jozef Kozisek, Marian Gall, Stanislav Biskupic, Marek Fronc, Katharina Schiessl, Olesea Cuzan, Denis Prodius, Constantin Turta, Sergiu Shova, Dariusz A. Zajac, Vladimir Arion
Abstrakt

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.

Organisation(en)
Institut für Anorganische Chemie, Institut für Organische Chemie
Externe Organisation(en)
Slovak University of Technology in Bratislava, Czech Academy of Sciences, Academy of Sciences of the Republic of Moldova, Helmholtz-Zentrum Berlin für Materialien und Energie
Journal
European Journal of Inorganic Chemistry
Band
14
Seiten
2505-2519
Anzahl der Seiten
15
ISSN
1434-1948
DOI
https://doi.org/10.1002/ejic.201201526
Publikationsdatum
2013
Peer-reviewed
Ja
ÖFOS 2012
104003 Anorganische Chemie
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/b5725408-761a-4f70-a07e-54d302f1aebc

Publikationen

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

Autor(en)
Lukas Bucinsky, Gabriel Büchel, Robert Ponec, Peter Rapta, Martin Breza, Jozef Kozisek, Marian Gall, Stanislav Biskupic, Marek Fronc, Katharina Schiessl, Olesea Cuzan, Denis Prodius, Constantin Turta, Sergiu Shova, Dariusz A. Zajac, Vladimir Arion
Abstrakt

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.

Organisation(en)
Institut für Anorganische Chemie, Institut für Organische Chemie
Externe Organisation(en)
Slovak University of Technology in Bratislava, Czech Academy of Sciences, Academy of Sciences of the Republic of Moldova, Helmholtz-Zentrum Berlin für Materialien und Energie
Journal
European Journal of Inorganic Chemistry
Band
14
Seiten
2505-2519
Anzahl der Seiten
15
ISSN
1434-1948
DOI
https://doi.org/10.1002/ejic.201201526
Publikationsdatum
2013
Peer-reviewed
Ja
ÖFOS 2012
104003 Anorganische Chemie
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/b5725408-761a-4f70-a07e-54d302f1aebc

Vortraege

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

Autor(en)
Lukas Bucinsky, Gabriel Büchel, Robert Ponec, Peter Rapta, Martin Breza, Jozef Kozisek, Marian Gall, Stanislav Biskupic, Marek Fronc, Katharina Schiessl, Olesea Cuzan, Denis Prodius, Constantin Turta, Sergiu Shova, Dariusz A. Zajac, Vladimir Arion
Abstrakt

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.

Organisation(en)
Institut für Anorganische Chemie, Institut für Organische Chemie
Externe Organisation(en)
Slovak University of Technology in Bratislava, Czech Academy of Sciences, Academy of Sciences of the Republic of Moldova, Helmholtz-Zentrum Berlin für Materialien und Energie
Journal
European Journal of Inorganic Chemistry
Band
14
Seiten
2505-2519
Anzahl der Seiten
15
ISSN
1434-1948
DOI
https://doi.org/10.1002/ejic.201201526
Publikationsdatum
2013
Peer-reviewed
Ja
ÖFOS 2012
104003 Anorganische Chemie
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/b5725408-761a-4f70-a07e-54d302f1aebc