Abstract
The reaction of metal hexafluoroacetylacetonates M(hfac)2, where M = Fe, Mn, and Co, with 3,6-di-tert-butyl-o-benzoquinone (3,6-Q) in the inert atmosphere of a dry box is found to yield mixed-ligand complexes [M(hfac)2(3,6-Q)]. When the synthesis is performed under ambient conditions or the [M(hfac)2(3,6-Q)] mother liquor is kept in air in the case of Mn(II) and Co(II), crystals of [M(hfac)2(H2O)2](3,6-Q) aqua complexes precipitate into the solid phase, in which cis-coordinated H2O molecules are hydrogen bonded to o-quinone O atoms. Single crystal X-ray diffraction data for compounds, which correlate with the results of quantum chemical calculations, show that solid [M(hfac)2(3,6-Q)] and [M(hfac)2(H2O)2](3,6-Q), where M = Co(II) and Mn(II), contain initial o-quinone molecules. In the interaction of Fe(hfac)2 with 3,6-Q, there is an intramolecular redox process during which Fe(II) is oxidized to Fe(III) and o-quinone is reduced to the respective semiquinonate radical anion, which leads to the formation of [FeIII(hfac)2(3,6-SQ)]. According to the data of magnetic measurements, a strong antiferromagnetic exchange between high-spin Fe(III) unpaired electrons and SQ provide an almost complete compensation of spin of one of the unpaired electrons of the metal ion by SQ spin. For Co a complex with 3,5-di-tert-butyl-o-benzoquinone [Co(hfac)2(3,5-Q)] is also synthesized and its structure and magnetic properties are studied. The latter prove to be similar to those of [Co(hfac)2(3,6-Q)].
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References
C. G. Pierpont. Inorg. Chem., 2011, 50(20), 9766–9772.
K. Martyanov and V. Kuropatov. Inorganics, 2018, 6(2), 48.
D. L. Broere, R. Plessius, and J. I. van der Vlugt. Chem. Soc. Rev., 2015, 44(19), 6886–6915.
A. A. Starikova and V. I. Minkin. Russ. Chem. Rev., 2018, 87(11), 1049–1079.
S. Agake, H. Komatsuzaki, M. Satoh, T. Agou, Y. Tanaka, M. Akita, J. Nakazawa, and S. Hikichi. Inorg. Chim. Acta, 2019, 484(1), 424–429.
G. Ulas, T. Lemmin, Y. Wu, G. T. Gassner, and W. F. DeGrado. Nat. Chem., 2016, 8, 354–359.
V. I. Ovcharenko, E. V. Gorelik, S. V. Fokin, G. V. Romanenko, V. N. Ikorskii, A. V. Krashilina, V. K. Cherkasov, and G. A. Abakumov. J. Amer. Chem. Soc., 2007, 129, 10512–10521.
J. F. Gonzalez, O. Cador, L. Ouahab, S. Norkov, V. Kuropatov, and F. Pointillart. Inorganics, 2018, 6(2), 45.
A. I. Poddel’sky, V. K. Cherkasov, and G. A. Abakumov. Coord. Chem. Rev., 2009, 253, 291–324.
C. Roux, D. M. Adams, J. P. Itié, A. Polian, D. N. Hendrickson, and M. Verdaguer. Inorg. Chem., 1996, 35(10), 2846–2852.
C. Boskovic. In: Spin-Crossover Materials — Properties and Applications/Ed. M. A. Halcrow. John Wiley & Sons: Chichester, 2013, 203–224.
T. Tezgerevska, K. G. Alley, and C. Boskovic. Coord. Chem. Rev., 2014, 268, 23–40.
J. Overgaard, L. H. Møller, M. A. Borup, M. Tricoire, J. P. S. Walsh, M. Diehl, and E. Rentschler. Dalton Trans., 2016, 45, 12924–12932.
Cambridge Structural Database System, Version 5.40, 2018 (updates Aug. 2019).
G. V. Romanenko, S. V. Fokin, D. P. Pischur, A. S. Bogomyakov, and V. I. Ovcharenko. J. Struct. Chem., 2019, 60(10), 1696–1700.
V. I. Minkin, A. A. Starikova, and R. M. Minyaev. Dalton Trans., 2013, 42, 1726–1734.
A. A. Starikova. Quantum-Chemical Modeling of Spin Transitions and Exchange Interactions in Metal Complexes with Redox Active Ligands [in Russian]. Doctoral (Phys.-Math. 02.00.04) Dissertation, Rostov-on-Don, South Fedrral University, 2019, 300.
G. M. Sheldrick. Acta Crystallogr., 2015, C71, 3–8.
P. Giannozzi, O. Andreussi, T. Brumme, O. Bunau, M. Buongiorno Nardelli, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, M. Cococcioni, N. Colonna, I. Carnimeo, A. Dal Corso, S. de Gironcoli, P. Delugas, R. A. DiStasio Jr., A. Ferretti, A. Floris, G. Fratesi, G. Fugallo, R. Gebauer, U. Gerstmann, F. Giustino, T. Gorni, J. Jia, M. Kawamura, H.-Y. Ko, A. Kokalj, E. Küçükbenli, M. Lazzeri, M. Marsili, N. Marzari, F. Mauri, N. L. Nguyen, H.-V. Nguyen, A. Otero-de-la-Roza, L. Paulatto, S. Poncé, D. Rocca, R. Sabatini, B. Santra, M. Schlipf, A. P. Seitsonen, A. Smogunov, I. Timrov, T. Thonhauser, P. Umari, N. Vast, X. Wu, and S. Baroni. J. Phys.: Condens. Matter, 2017, 29, 465901.
M. F. Sgroi, R. Lazzaroni, D. Beljonne, and D. Pull. Batteries, 2017, 3(2), 11.
V. A. Morozov, M. V. Petrova, and N. N. Lukzen. AIP Adv., 2015, 5, 087161.
S. N. Brown. Inorg. Chem., 2012, 51, 1251–1260.
L. Noodleman. J. Chem. Phys., 1981, 74, 5737–5743.
Acknowledgments
G.V. Romanenko is thankful to RFBR for supporting the structural studies (grant 19-29-08005). A.S. Bogomyakov is thankful to the Siberian Branch of the Russian Academy of Sciences for supporting the magnetochemical measurements (grant II.1.7.3).
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This research was supported by Russian Scientific Foundation grant 18-13-00380.
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Russian Text © The Author(s), 2020, published in Zhurnal Strukturnoi Khimii, 2020, Vol. 61, No. 4, pp. 571–579.
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Fokin, S.V., Fursova, E.Y., Letyagin, G.A. et al. Structure and Magnetic Properties of Mixed-Ligand Complexes of 3d Metal Hexafluoroacetylacetonates with 3,5- and 3,6-Di-Tert-Butyl-O-Benzoquinones. J Struct Chem 61, 541–549 (2020). https://doi.org/10.1134/S002247662004006X
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DOI: https://doi.org/10.1134/S002247662004006X