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Article

Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors

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Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia
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Department of General and Inorganic Chemistry, Gubkin Russian State University of Oil and Gas (National Research University), 119991 Moscow, Russia
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Sara Pharm Solutions S.R.L., 266-268 Calea Rahovei, 050912 Bucharest, Romania
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Department of Analytical Chemistry, University of Vienna, Währinger Strasse 38, A-1090 Vienna, Austria
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Institute of Physical Chemistry and Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovakia
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Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
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Institute of Inorganic Chemistry, University of Vienna, Währinger Strasse 42, A-1090 Vienna, Austria
*
Authors to whom correspondence should be addressed.
Academic Editor: Nikolay Gerasimchuk
Molecules 2021, 26(2), 336; https://doi.org/10.3390/molecules26020336
Received: 13 December 2020 / Revised: 1 January 2021 / Accepted: 4 January 2021 / Published: 11 January 2021
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and hafnium(IV) phthalocyaninate-capped derivatives. Electronic structures of their 1e-oxidized and 1e-electron-reduced forms were experimentally studied by electron paramagnetic resonance (EPR) spectroscopy and UV−vis−near-IR spectroelectrochemical experiments and supported by density functional theory (DFT) calculations. The investigated hybrid molecular systems that combine a transition metal (pseudo)clathrochelate and a Zr/Hf-phthalocyaninate moiety exhibit quite rich redox activity both in the cathodic and in the anodic region. These binuclear compounds and their precursors were tested as potential catalysts in oxidation reactions of cyclohexane and the results are discussed. View Full-Text
Keywords: clathrochelates; phthalocyanines; zirconium(IV); hafnium(IV); nickel(II); iron(II); spectroelectrochemistry; homogeneous catalysis; oxidation reactions; DFT calculations clathrochelates; phthalocyanines; zirconium(IV); hafnium(IV); nickel(II); iron(II); spectroelectrochemistry; homogeneous catalysis; oxidation reactions; DFT calculations
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MDPI and ACS Style

Voloshin, Y.Z.; Dudkin, S.V.; Belova, S.A.; Gherca, D.; Samohvalov, D.; Manta, C.-M.; Lungan, M.-A.; Meier-Menches, S.M.; Rapta, P.; Darvasiová, D.; Malček, M.; Pombeiro, A.J.L.; Martins, L.M.D.R.S.; Arion, V.B. Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors. Molecules 2021, 26, 336. https://doi.org/10.3390/molecules26020336

AMA Style

Voloshin YZ, Dudkin SV, Belova SA, Gherca D, Samohvalov D, Manta C-M, Lungan M-A, Meier-Menches SM, Rapta P, Darvasiová D, Malček M, Pombeiro AJL, Martins LMDRS, Arion VB. Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors. Molecules. 2021; 26(2):336. https://doi.org/10.3390/molecules26020336

Chicago/Turabian Style

Voloshin, Yan Z., Semyon V. Dudkin, Svetlana A. Belova, Daniel Gherca, Dumitru Samohvalov, Corina-Mihaela Manta, Maria-Andreea Lungan, Samuel M. Meier-Menches, Peter Rapta, Denisa Darvasiová, Michal Malček, Armando J.L. Pombeiro, Luísa M.D.R.S. Martins, and Vladimir B. Arion 2021. "Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors" Molecules 26, no. 2: 336. https://doi.org/10.3390/molecules26020336

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