Easily electroreducible halogen-free germanium complexes with biologically active pyridines

[Display omitted] •The conversion of GeO2 into soluble non-halogenated forms occurs smoothly and in high yields.•The formed complexes (DTBC)2GeL2 (L = nicotinic acid, nicotinamide and isoniazid) are air stable.•These complexes are easily reducible at the cathodic potentials in comparison with initia...

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Bibliographic Details
Published in:Inorganica Chimica Acta 2019-09, Vol.495, p.119007, Article 119007
Main Authors: Nikolaevskaya, Elena N., Shangin, Pavel G., Starikova, Alyona A., Jouikov, Viatcheslav V., Egorov, Mikhail P., Syroeshkin, Mikhail A.
Format: Article
Language:English
Subjects:
Catechols
Chemical reduction
Chemical Sciences
Cyclic voltammetry
DFT calculations
Germanium
Germanium dioxide
Germanium oxides
Glassy carbon
Ligands
Nicotinamide
Nicotinic acid
Pyridines
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Summary:[Display omitted] •The conversion of GeO2 into soluble non-halogenated forms occurs smoothly and in high yields.•The formed complexes (DTBC)2GeL2 (L = nicotinic acid, nicotinamide and isoniazid) are air stable.•These complexes are easily reducible at the cathodic potentials in comparison with initial ligands L.•The ease of electroreduction are in good agreement with DFT B3LYP/def2tzvp analysis. The green conversion of germanium dioxide into soluble non-halogenated forms suitable for further processing occurs smoothly and in high yields under the action of 3,5-di-tert-butylbenzene-1,2-diol in presence of biologically active N-donor ligands L. The formed hexacoordinated germanium catecholate complexes (DTBCat)2GeL2 (DTBCat = 3,5-di-tert-butylcatecholate, L = nicotinic acid, nicotinamide and isoniazid) 1–3 are air stable and soluble in common organic solvents. These new complexes are easily reducible at a glassy carbon electrode in DMF/0.1 M Bu4NBF4 at the cathodic potentials remarkably less negative than those of the reduction of parent non-coordinated N-donor ligands L; the corresponding anodic shifts for 1–3 are 0.598, 1.009 and 0.978 V, respectively. The ease of the electrochemical reduction and the energy of electron donation from the ligands L to germanium in 1–3 are in good agreement with DFT B3LYP/def2tzvp analysis and the stabilization energies of these germanium complexes.
ISSN:0020-1693
1873-3255
0020-1693
DOI:10.1016/j.ica.2019.119007