Papers by Viatcheslav Jouikov
Carbon, 2019
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Russian Chemical Reviews, 2018
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Journal de Chimie Physique, 1996
ABSTRACT
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ECS Transactions, 2010
Electrooxidation of all-five and all-six membered metallatranes (M = Si, Ge) derivatives of triet... more Electrooxidation of all-five and all-six membered metallatranes (M = Si, Ge) derivatives of triethanolamine, and those with aryl-fused lateral chains (derivatives of 2,2',2"-nitrilotriphenol and 2,2',2'-nitrilotris(methylene) triphenol) was studied by cyclic voltammetry and EPR-spectroelectro¬chemistry supported by DFT B3LYP/ LANL2DZ calculations. Phenyl and vinyl metallatranes form distonic cation radicals which are more stable than those of triorganyl amino precursors, and can be observed in acetonitrile already at 250 K. EPR-spectroelectrochemistry revealed that spin density in these species is mainly localized on the axially directed and pointed inside the atrane cage pz orbital of nitrogen. Both EPR and Fermi contact coupling from DFT B3LYP/LANL2DZ calculations have shown zero contribution from the metal in the spin delocalization in these species. DFT calculations suggest that the N atom in these cation radicals is practically planar; Ge atom configuration fla...
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ChemInform, 2010
ABSTRACT
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Chemistry (Weinheim an der Bergstrasse, Germany), Jan 21, 2014
Covalent Si-C grafting of a silatrane cage to a carbon-based interface provides a truly conjugate... more Covalent Si-C grafting of a silatrane cage to a carbon-based interface provides a truly conjugated benzyl-type system in which the 3 c-4 e orbital of the silatrane interacts with the macroscopic π-type substituent (graphite Csp2 network) through hyperconjugation. This process, studied by voltammetry, EIS, FTIR, SEM and DFT modeling, allows one to build carbon-based conducting interfaces with electronically conjugated molecular extensions. Non-conjugated covalent grafting of an alkyl silatrane moiety provides chemically stable functional interfaces that have good promise for electrochemically-driven applications, for example, electrochemical spin-writing.
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ECS Transactions, 2008
Electrochemistry of organic derivatives of silicon started more than 30 years ago with the reduct... more Electrochemistry of organic derivatives of silicon started more than 30 years ago with the reductive cleavage of Si-Cl bonds. Since then, silyl anions - primary intermediates of this process, - were extensively exploited to form disilanes and polysilanes. Recently it was shown that electrochemical activation of Si-Cl bonds under special conditions offers the opportunity to generate not only R3Si- species but a large palette of specific and highly reactive silicon intermediates as well such as silanones, silyl peroxides and silyl radicals. Electrogeneration of transient silanones prepared in situ from the basic starting material - chloro, alkoxy and alkylthiosilanes - allow functionalization of commercial siloxanes and polysiloxanes by inserting a new XYSiO fragment carrying various organic functional groups (X,Y) into the backbone of the target siloxane. Silyl radicals, electrochemically produced by different ways, make possible direct silylation of unsaturated compounds. Electroche...
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ECS Transactions, 2008
Silicon-centered radicals R3Si•, both as short-lived intermediates and as persistent species, wer... more Silicon-centered radicals R3Si•, both as short-lived intermediates and as persistent species, were produced by means of electrochemistry. The one-electron electrochemical oxidation of silyl anions prepared by various methods (sonochemical cleavage of disilanes with K, reductive electrochemical titration of monochlorosilanes and by reverse electrochemistry in a flow-through cell) resulted in R3Si• radicals, which were involved in radical silylation of double bonds or trapped with PTBN as shown by EPR-spectroelectrochemistry. The same radical species were produced by oxidation-reduction of hexaphenyldisilane in a flow-through teo-compartment cell. The possibility of generating silyl radicals by direct one-electron cathodic reduction has been demonstrated.
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An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
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Journal of Organometallic Chemistry, 2022
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Journal of Organometallic Chemistry, 2018
International audienceBenzophenones (BPs) of the type 2-R-BP and 2,2'-R-BP, carrying silicon-... more International audienceBenzophenones (BPs) of the type 2-R-BP and 2,2'-R-BP, carrying silicon-or germanium-containing substituents R (R = EY2X; E = Si, Ge; Y = H, Me, F, Cl; X = H, F, Cl, OTf) at one or at two ortho-positions of the arene rings, were theoretically designed. Among 26 compounds considered, only 10 monosubstituted 2-R-BP and 5 bis-substituted 2,2'-R-BP (in hexane and DMSO solutions) belong to the first examples of hypervalent benzophenones. In these "true" chelates, the length of the O -> E dative contact (which has a covalent component, according to the AIM analysis) is in the range of 2.0-2.4 angstrom, and the degree of pentacoordination of E is higher than 40%. In these compounds, a significant planarization of the benzophenone part occurs, compared to the initial BP. The TD-DFT calculations suggest the UV spectral properties of the hypervalent BPs to differ fundamentally from those of BP. For the "true" chelates 2-R-BP and 2,2'-R-BP, there is a well pronounced trend of a change of the coordination O -> E contact strength along with the difference between the wavelengths of their first high-intensity band and the pi pi* band of the unsubstituted BP. (c) 2018 Elsevier B.V. All rights reserved
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Synthesis, 2018
Novel fused bis-germatranes containing three hypercoordinated atoms (two Ge and one N) and substi... more Novel fused bis-germatranes containing three hypercoordinated atoms (two Ge and one N) and substituted at the 1,1′-positions with bromo-thienyl groups [(3-bromo-2-thienyl)-, (3,5-dibromo-2-thienyl)-, and 3-(4-bromo)-2-thienyl] have been synthesized from the corresponding triethoxy(thienyl)germanes and tris(1,3-dihydroxypropan-2-yl)amine. The doubly degenerated HOMO and HOMO-1 in these compounds are localized on the thienyl substituents while a 5c-6e hyperbond of the bis-germatranyl core (C–Ge←N→Ge–C system) is only a lower lying HOMO-2. Square-wave pulse voltammetry in CH3CN/0.1 M Bu4NPF6 shows all three compounds to undergo reversible electrochemical oxidation affecting one thienyl substituent. The DFT B3LYP/Lanl2DZ//HF/6-311G(d,p) calculations of their cation radicals suggest the enhancement and shortening of the N→Ge intramolecular dative bond on the side of the oxidized thienyl unit because of the positive charge and the increased acceptor character of the latter; this is accomp...
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Dalton Transactions, 2017
Electrochemical oxidation of phenyl silatrane provides persistent radical cations with an unpaire... more Electrochemical oxidation of phenyl silatrane provides persistent radical cations with an unpaired electron mostly localized on the atrane nitrogen.
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Papers by Viatcheslav Jouikov