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  The Ruthenium Nitrosyl Moiety in Clusters: Trinuclear Linear μ-Hydroxido Magnesium(II)-Diruthenium(II), μ3-Oxido Trinuclear Diiron(III)–Ruthenium(II), and Tetranuclear μ4-Oxido Trigallium(III)-Ruthenium(II) Complexes

Stepanenko, I., Mizetskyi, P., Orlowska, E., Bučinský, L., Zalibera, M., Vénosová, B., et al. (2022). The Ruthenium Nitrosyl Moiety in Clusters: Trinuclear Linear μ-Hydroxido Magnesium(II)-Diruthenium(II), μ3-Oxido Trinuclear Diiron(III)–Ruthenium(II), and Tetranuclear μ4-Oxido Trigallium(III)-Ruthenium(II) Complexes. Inorganic Chemistry, 61(2), 950-967. doi:10.1021/acs.inorgchem.1c03011.

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Stepanenko, Iryna1, Author
Mizetskyi, Pavlo1, Author
Orlowska, Ewelina1, Author
Bučinský, Lukáš2, Author
Zalibera, Michal2, Author
Vénosová, Barbora2, 3, Author
Clémancey, Martin4, Author
Blondin, Geneviève4, Author
Rapta, Peter2, Author
Novitchi, Ghenadie5, Author
Schrader, Wolfgang6, Author              
Schaniel, Dominik7, Author
Chen, Yu-Sheng8, Author
Lutz, Martin9, Author
Kožíšek, Jozef2, Author
Telser, Joshua10, Author
Arion, Vladimir B.1, Author
1University of Vienna, Institute of Inorganic Chemistry, Währinger Strasse 42, A-1090 Vienna, Austria, ou_persistent22              
2Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovak Republic, ou_persistent22              
3Department of Physics, Faculty of Science, University of Ostrava, 30. dubna 22, 70103 Ostrava, Czech Republic, ou_persistent22              
4Univ. Grenoble Alpes, CNRS, CEA, IRIG, LCBM, F-38000 Grenoble, France, ou_persistent22              
5CNRS-LNCMI, 17 avenue des Martyrs, 38042 Grenoble Cedex, France, ou_persistent22              
6Service Department Schrader (MS), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445629              
7Université de Lorraine, CNRS, CRM2, 54506 Nancy, France, ou_persistent22              
8NSF’s ChemMATCARS, The University of Chicago, Lemont, Illinois 60439, United States, ou_persistent22              
9Structural Biochemistry, Bijvoet Centre for Biomolecular Research, Utrecht University, 3584 CH Utrecht, The Netherlands, ou_persistent22              
10Department of Biological, Physical and Health Sciences, Roosevelt University, 430 South Michigan Avenue, Chicago, Illinois 60605, United States, ou_persistent22              


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 Abstract: The ruthenium nitrosyl moiety, {RuNO}6, is important as a potential releasing agent of nitric oxide and is of inherent interest in coordination chemistry. Typically, {RuNO}6 is found in mononuclear complexes. Herein we describe the synthesis and characterization of several multimetal cluster complexes that contain this unit. Specifically, the heterotrinuclear μ3-oxido clusters [Fe2RuCl43-O)(μ-OMe)(μ-pz)2(NO)(Hpz)2] (6) and [Fe2RuCl33-O)(μ-OMe)(μ-pz)3(MeOH)(NO)(Hpz)][Fe2RuCl33-O)(μ-OMe)(μ-pz)3(DMF)(NO)(Hpz)] (7·MeOH·2H2O) and the heterotetranuclear μ4-oxido complex [Ga3RuCl34-O)(μ-OMe)3(μ-pz)4(NO)] (8) were prepared from trans-[Ru(OH)(NO)(Hpz)4]Cl2 (5), which itself was prepared via acidic hydrolysis of the linear heterotrinuclear complex {[Ru(μ-OH)(μ-pz)2(pz)(NO)(Hpz)]2Mg} (4). Complex 4 was synthesized from the mononuclear Ru complexes (H2pz)[trans-RuCl4(Hpz)2] (1), trans-[RuCl2(Hpz)4]Cl (2), and trans-[RuCl2(Hpz)4] (3). The new compounds 4–8 were all characterized by elemental analysis, ESI mass spectrometry, IR, UV–vis, and 1H NMR spectroscopy, and single-crystal X-ray diffraction, with complexes 6 and 7 being characterized also by temperature-dependent magnetic susceptibility measurements and Mössbauer spectroscopy. Magnetometry indicated a strong antiferromagnetic interaction between paramagnetic centers in 6 and 7. The ability of 4 and 6–8 to form linkage isomers and release NO upon irradiation in the solid state was investigated by IR spectroscopy. A theoretical investigation of the electronic structure of 6 by DFT and ab initio CASSCF/NEVPT2 calculations indicated a redox-noninnocent behavior of the NO ancillary ligand in 6, which was also manifested in TD-DFT calculations of its electronic absorption spectrum. The electronic structure of 6 was also studied by an X-ray charge density analysis.


Language(s): eng - English
 Dates: 2021-09-262021-12-282022-01-17
 Publication Status: Published in print
 Pages: 18
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.1c03011
 Degree: -



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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 61 (2) Sequence Number: - Start / End Page: 950 - 967 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669