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, Iryna; Mizetskyi, Pavlo; Orlowska, Ewelina; Bučinský, Lukáš; Zalibera, Michal; Vénosová, Barbora; Clémancey, Martin; Blondin, Geneviève; Rapta, Peter; Novitchi, Ghenadie; Schrader, Wolfgang; Schaniel, Dominik; Chen, Yu-Sheng; Lutz, Martin; Kožíšek, Jozef; Telser, Joshua; Arion, Vladimir B.

doi:10.1021/acs.inorgchem.1c03011

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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

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Schrader, Wolfgang
Service Department Schrader (MS), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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引用

Stepanenko, I., Mizetskyi, P., Orlowska, E., Bučinský, L., Zalibera, M., Vénosová, B., Clémancey, M., Blondin, G., Rapta, P., Novitchi, G., Schrader, W., Schaniel, D., Chen, Y.-S., Lutz, M., Kožíšek, J., Telser, J., & Arion, V. B. (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.

引用: https://hdl.handle.net/21.11116/0000-000A-2C4E-F

要旨

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 [Fe₂RuCl₄(μ₃-O)(μ-OMe)(μ-pz)₂(NO)(Hpz)₂] (6) and [Fe₂RuCl₃(μ₃-O)(μ-OMe)(μ-pz)₃(MeOH)(NO)(Hpz)][Fe₂RuCl₃(μ₃-O)(μ-OMe)(μ-pz)₃(DMF)(NO)(Hpz)] (7·MeOH·2H₂O) and the heterotetranuclear μ₄-oxido complex [Ga₃RuCl₃(μ₄-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.