A5032863224- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Silicone and Siloxane Chemistry
- Magnetism in coordination complexes
- Polyoxometalates: Synthesis and Applications
- Metal-Organic Frameworks: Synthesis and Applications
- Organometallic Compounds Synthesis and Characterization
- Lanthanide and Transition Metal Complexes
- Crystallography and molecular interactions
- Catalytic Processes in Materials Science
- Organometallic Complex Synthesis and Catalysis
- Analytical Chemistry and Sensors
- Supramolecular Chemistry and Complexes
- Inorganic Fluorides and Related Compounds
- Porphyrin and Phthalocyanine Chemistry
- Catalysis and Oxidation Reactions
- Synthesis and characterization of novel inorganic/organometallic compounds
- Electron Spin Resonance Studies
- Metal and Thin Film Mechanics
- Vanadium and Halogenation Chemistry
- Metal-Catalyzed Oxygenation Mechanisms
- Inorganic and Organometallic Chemistry
- Diamond and Carbon-based Materials Research
- Oxidative Organic Chemistry Reactions
- Marine Biology and Environmental Chemistry
A. N. Nesmeyanov Institute of Organoelement Compounds
2008-2021
Russian Academy of Sciences
2008-2018
Centre National de la Recherche Scientifique
2015
Semenov Institute of Chemical Physics
1995-2015
Institut des Biomolécules Max Mousseron
2015
Université de Montpellier
2015
École Nationale Supérieure de Chimie de Montpellier
2015
A.V. Topchiev Institute of Petrochemical Synthesis
1995
Two principally different in their molecular architecture isomeric tetranuclear copper(ii) silsesquioxanes, "Globule"-like compound [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1) and "Sandwich"-like derivative [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (2), were synthesized by the partial cleavage of polymeric silsesquioxane [(PhSiO1.5)2(CuO)]n tetraphenylcyclotetrasiloxanolate. The route leading to formation either 1 or 2 entirely depends on nature composition solvent used for this reaction. Thus, process...
Abstract The transmetalation of bimetallic copper–sodium silsesquioxane cages, namely, [(PhSiO 1.5 ) 10 (CuO) 2 (NaO 0.5 ] (“Cooling Tower”; 1 ), 12 4 (“Globule”; and 6 (PhSiO (“Sandwich”; 3 resulted in the generation three types hexanuclear cylinder‐like copper silsesqui‐ oxanes, (C H 9 OH) 5 ( 8 O (PhCN) (MeOH) (NaCl)(C (H O) ). products show a prominent “solvating system–structure” dependency, as determined by X‐ray diffraction. Topological analysis cages – was also performed. In...
Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO1.5)18(CuO)9] 1, hexa- [(MeSiO1.5)10(HO0.5)2(CuO)6(C12H8N2)2(MeSiO1.5)10(HO0.5)1.33(CH3COO0.5)0.67(CuO)6(C12H8N2)2] 2, [(MeSiO1.5)10(CuO)6(MeO0.5)2(C10H8N2)2] 3, and trinuclear [(MeSiO1.5)8(CuO)3(C10H8N2)2] 4, were obtained in 44%, 27%, 20%, 16% yields, respectively. Nuclearity structural fashion products was controlled by the choice solvent system ligand, specifically assisting assembling cage. Structures...
The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO<sub>1.5</sub>)<sub>20</sub>(FeO<sub>1.5</sub>)<sub>6</sub>(NaO<sub>0.5</sub>)<sub>8</sub>(<italic>n</italic>-BuOH)<sub>9.6</sub>(C<sub>7</sub>H<sub>8</sub>)] (<bold>I</bold>) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses DFT calculation.
The current status of the chemistry metallasiloxanes is surveyed. Synthetic methods affording metallasiloxane fragments and specific transformations governed by coordination properties metal site are analysed. emphasis placed onto formation compounds with rearrangements these fragments. Principles design catalytic systems based on metallasiloxanes, in particular, containing low-coordinated sites, generalised.
Abstract A new method of metallasilsesquioxane synthesis is described for the first time. According to this method, a partial nucleophilic cleavage polymeric copper phenylsilsesquioxane by use sym‐cis ‐tetraphenylcyclotetrasiloxanolate nonaethanolate ( 1 ) gave previously unknown binuclear cage‐like silsesquioxane [(PhSiO 1.5 10 (CuO) 2 (NaO 0.5 · 4EtOH] ). The unprecedented structure , so called “Cooling Tower” structure, was confirmed single‐crystal X‐ray diffraction analysis. Compound...
Copper(<sc>ii</sc>) silsesquioxanes [(PhSiO<sub>1.5</sub>)<sub>12</sub>(CuO)<sub>4</sub>(NaO<sub>0.5</sub>)<sub>4</sub>] or [(PhSiO<sub>1.5</sub>)<sub>10</sub>(CuO)<sub>2</sub>(NaO<sub>0.5</sub>)<sub>2</sub>] are catalysts for alkane oxidation with H<sub>2</sub>O<sub>2</sub>or<italic>t</italic>-BuOOH.
Cage-like Ni(<sc>ii</sc>)-silsesquioxanes demonstrate the presence of a slow relaxation magnetization, induced by spin glass-like behavior.
A new pentanuclear "cylinder"-like cobalt(ii) phenylsilsesquioxane [(PhSiO1.5)10(CoO)5(NaOH)] exhibits a slow relaxation of the magnetization and high catalytic activity stereoselectivity in oxidation alkanes alcohols.
Unusual high-cluster (Cu9) cage phenylsilsesquioxanes were obtained via complexation of in situ CuII,Na-silsesquioxane species formed with phenanthroline and neocuproine. In the first case, phenanthroline, acting as "a silent ligand" (not participating composition final product), favors formation an unprecedented cagelike phenylsilsesquioxane Cu9Na6 nuclearity, 1. second neocuproine ligands withdraws two Cu ions from metallasilsesquioxane matrix, producing cationic fragments...
Abstract A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type molecular topology consisting the hexairon oxo {Fe 6 O 19 } core surrounded in triangular manner by three cyclic germoxanolates [PhGe(O)O] 5 . This structural organization induces antiferromagnetic interactions between Fe III ions through oxygen atoms. Evaluated for this first time catalysis, these compounds showed high catalytic activity oxidation...
Abstract A heterometallic phenylsilsesquioxane [(PhSiO 1,5 ) 22 (CoO) 3 (NaO 0.5 6 ]⋅(EtOH) ⋅(H 2 O) 1 cage architecture of Co II ions in a triangular topology exhibits slow dynamic behavior its magnetization, induced by the freezing spins individual molecules.
Two types of heterometallic (Fe(III),Na) silsesquioxanes—[Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)4.5.1.25(MeCN), I, and [Ph5Si5O10]2[Ph4Si4O8]2Fe6Na6(O2‒)3(MeCN)8.5(H2O)8.44, II—were obtained characterized. X-ray studies established distinctive structures both products, with pair Fe(III)-O-based triangles surrounded by siloxanolate ligands, giving fascinating cage architectures. Complex II proved to be catalytically active in the formation amides from alcohols amines, thus...
A new family of bi-, tetra-, penta-, and hexanickel cagelike phenylsilsesquioxanes 1–6 was obtained by self-assembly transmetalation procedures. Their crystal structures were established single-crystal X-ray analysis, features packing relevant to the network formation studied a topological analysis. Compounds 1, 2, 4 are isolated architectures, while 3, 5, 6 present extended 1D 3D networks. The investigation magnetic properties revealed presence ferro- (1 3–5) or antiferromagnetic (2 6)...
The synthesis, composition, and catalytic properties of a new family hexanuclear Cu(II)-based phenylsilsesquioxanes are described here. Structural studies 17 synthesized compounds revealed the general principle underlying their molecular topology: viz., central metal oxide layer consisting two Cu3 trimers is coordinated by cyclic [PhSiO1.5]5 siloxanolate ligands to form skewed sandwich architecture with composition [(PhSiO1.5)10(CuO)6]2+. In addition this O ligation rings, opposite copper...
Abstract Herein, we describe an approach to cage metallasilsesquioxanes by self‐assembly with 1,2‐bis(diphenylphosphino)ethane as a key reactant. This allowed us achieve unique family of complexes that includes anionic tetra‐ and nonanuclear copper(II) sodium silsesquioxane cationic copper(I) components. Additional representatives this intriguing metallasilsesquioxane (Cu 9 Na 6 Cu 3 Cs ) were obtained through the replacement original ethanol‐based reaction medium DMSO. The fascinating...
New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)6(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)6(NaCl)(C4H8O2)13(PhCN)2(H2O)2 and studied by X-ray topological analysis. The compound exhibits cylinder-like type of molecular architecture represents very rare case polyhedral complexation metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation such small molecules light alkanes alcohols. Namely, oxidation...
Herein, the effect of replacement surrounding solvent and/or partial substitution sodium ions in cage-like copper, phenylsilsesquioxane [(PhSiO1.5)12(CuO)4(NaO0.5)4(n-BuOH)6] 1 with a globular structure was investigated; synthesis ten new derivatives complex performed, and their crystal structures were determined. Solvate n-butanol dimethyl sulfoxide, acetonitrile, 1,4-dioxane/EtOH, 1,4-dioxane/PhCN afforded complexes [(PhSiO1.5)12(CuO)4(NaO0.5)4(DMSO)8] (2),...
The self-assembly synthesis of Cu(II)-silsesquioxane involving 2,9-dimethyl-1,10-phenanthroline (neocuproine) as an additional N ligand at copper atoms was performed. reaction revealed unprecedented aerobic hydroxylation only one the two methyl groups in neocuproine to afford corresponding geminal diol. produced derivative oxidized acts a two-centered N,O assembly hexacopper cage product [Cu6(Ph5Si5O10)2·(C14H11N2O2)2] (1), coordinating six centers product. Two siloxanolate ligands...