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REDUCTION PROPERTIES OF GERMANIUM DICHLORIDE WITH RESPECT TO THE REDOX-ACTIVE MONOIMINOACENAPHTENONE dpp-MIAN

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Abstract

Reaction of germanium dichloride [GeCl2(dioxane)] with 2-(2,6-diisopropylphenyl-imino)acenaphthylene-1-one (dpp-MIAN) leads to the reduction of dpp-MIAN and subsequent formation of the dianion bis-dpp-MIAN double ligand. Depending on the solvent, different products are formed. For example, reaction in toluene and diethyl ether yields digermylene [{(bis-dpp-MIAN)Ge(II)}Ge(II)Cl2] (1) where the doubled ligand is bonded to the divalent germanium atom by oxygen atoms, while the GeCl2 species is coordinated by an oxygen atom. Complex 1 forms two polymorphs, depending on crystallization conditions. Crystallization from toluene yields the 1m polymorph in the P2(1)/c monoclinic modification, while crystallization in diethyl ether yields the 1o polymorph in the Pbca orthorhombic modification. Reduction of dpp-MIAN by germanium dichloride in tetrahydrofuran yields the [(bis-dpp-MIAN)2Ge(IV)] complex (2) containing tetravalent germanium. Compounds 1 (polymorphs 1m and 1o) and 2 are characterized by IR spectroscopy, NMR, and XRD.

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Funding

This work was funded by the Russian Foundation for Basic Research (No.  20-03-00659) using equipment of the Collective Use Center “Analytical Center of IOMC RAS” within the project “Scientific Equipment for the Development of the Material and Technical Infrastructure of Common Use Centers” (identifier RF----2296.61321X0017, agreement No. 075-15-2021-670).

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  1. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

    A. N. Lukoyanov, Yu. V. Zvereva, G. Yu. Zhigulin, D. A. Razborov, E. V. Baranov & S. Yu. Ketkov

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Russian Text © The Author(s), 2023, published in Zhurnal Strukturnoi Khimii, 2023, Vol. 64, No. 2, 106292.https://doi.org/10.26902/JSC_id106292

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Lukoyanov, A.N., Zvereva, Y.V., Zhigulin, G.Y. et al. REDUCTION PROPERTIES OF GERMANIUM DICHLORIDE WITH RESPECT TO THE REDOX-ACTIVE MONOIMINOACENAPHTENONE dpp-MIAN. J Struct Chem 64, 288–301 (2023). https://doi.org/10.1134/S0022476623020130

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