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