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Halogen-free GeO2 conversion: electrochemical reduction vs. complexation in (DTBC)2Ge[Py(CN)n] (n = 0..2) complexes

Abstract

The 3,5-di-tert-butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0..2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n and characterized by elemental analysis, NMR, IR and UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has been determined by X-ray single crystal analysis. The UV-VIS spectra have shown these complexes to be stable in CH3CN, toluene and CH2Cl2 solutions; on the contrary, they are rapidly decomposed by dimethylformamide and tetrahydrofuran. Complexes 1 and 2 (with 4-cyano and 3-cyanopyridine) are electrochemically reducible in toluene/1 M Bu4NPF6 at E = -1.3…-1.7 V vs. AgCl. The quantum-chemical study of these complexes is in accordance with the unsuccessful attempts to obtain analogous derivatives with 2-cyanopyridine and 2,6-dicyanopyridine.

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Publication details

The article was received on 20 Aug 2018, accepted on 05 Nov 2018 and first published on 06 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT03397H
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Halogen-free GeO2 conversion: electrochemical reduction vs. complexation in (DTBC)2Ge[Py(CN)n] (n = 0..2) complexes

    E. Nikolaevskaya, E. Saverina, A. A. Starikova, A. Farhati, M. A. Kiskin, M. A. Syroeshkin, M. Egorov and V. Jouikov, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT03397H

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