A5039848511- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Oxidative Organic Chemistry Reactions
- Silicone and Siloxane Chemistry
- Metal-Catalyzed Oxygenation Mechanisms
- Polyoxometalates: Synthesis and Applications
- Vanadium and Halogenation Chemistry
- Magnetism in coordination complexes
- Organometallic Complex Synthesis and Catalysis
- Catalysis and Oxidation Reactions
- Metal complexes synthesis and properties
- Metal-Organic Frameworks: Synthesis and Applications
- Crystallography and molecular interactions
- Catalytic Processes in Materials Science
- Porphyrin and Phthalocyanine Chemistry
- Chemical Synthesis and Reactions
- Lanthanide and Transition Metal Complexes
- Organometallic Compounds Synthesis and Characterization
- Mesoporous Materials and Catalysis
- Radiopharmaceutical Chemistry and Applications
- Radioactive element chemistry and processing
- Asymmetric Hydrogenation and Catalysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Free Radicals and Antioxidants
- Catalysis for Biomass Conversion
A. N. Nesmeyanov Institute of Organoelement Compounds
2015-2024
Russian Academy of Sciences
2008-2019
Semenov Institute of Chemical Physics
1991
Abstract Trinuclear carbonyl hydride cluster, Os 3 (CO) 10 (µ‐H) 2 , catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The partly decomposes the course reaction afford cyclooctanone and cyclooctanol. Selectivity parameters obtained oxidations various linear branched alkanes as well kinetic features indicated that alkane occurs with participation hydroxyl radicals. A similar mechanism operates transformation benzene into phenol...
The heterometallic complex [Co(4)Fe(2)OSae(8)]·4DMF·H(2)O (1) was synthesized by one-pot reaction of cobalt powder with iron chloride in a dimethylformamide solution salicylidene-2-ethanolamine (H(2)Sae) and characterized single crystal X-ray diffraction analysis, magnetic measurements, high frequency electron paramagnetic resonance (HF-EPR), Mössbauer spectroscopies. exchange coupling the Fe(III)-Fe(III) pair is antiferromagnetic behavior J/hc = -190 cm(-1). HF-EPR spectra reveal an unusual...
Triosmium dodecacarbonyl catalyzes a very efficient oxidation of alkanes by H2O2 in MeCN to afford alkyl hydroperoxides (primary products) as well alcohols and ketones (aldehydes) at 60 °C if pyridine is added low concentration. Turnover numbers attain 000, turnover frequencies are up 24 000 h−1.
The efficient oxidation of alkanes (cyclohexane, n-heptane, methylcyclohexane, isooctane, cis- and trans-1,2-dimethylcyclohexane) to the corresponding alkyl hydroperoxides with system (n-Bu4N)[VO3]/H2O2/trifluoroacetic acid/MeCN–H2O was investigated in detail by 51V NMR, kinetic theoretical methods. It has been established on basis selectivity parameters linear branched peculiarities cyclohexane that reaction mechanism includes formation HO• radicals. presence acid (TFA) is crucial factor...
Six new copper(ii) complexes with 2,2':6',2''-terpyridine (4'-Rn-terpy) [1 (R1 = furan-2-yl), 2 (R2 thiophen-2-yl), and 3 (R3 1-methyl-1H-pyrrol-2-yl)] 2,6-di(thiazol-2-yl)pyridine derivatives (Rn-dtpy) [4 (R1), 5 (R2), 6 (R3)] have been synthesized by a reaction between chloride the corresponding ligand. The characterized UV-vis IR spectroscopy, their structures determined X-ray analysis. antiproliferative potential of towards human colorectal (HCT116) ovarian (A2780) carcinoma as well lung...
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...
Five monomeric oxovanadium(V) complexes [VO(OMe)(N∩O)2] with the nitro or halogen substituted quinolin-8-olate ligands were synthesized and characterized using Fourier transform infrared, 1H 13C NMR, high-resolution mass spectrometry-electrospray ionization as well X-ray diffraction UV-vis spectroscopy. These exhibit high catalytic activity toward oxidation of inert alkanes to alkyl hydroperoxides by H2O2 in aqueous acetonitrile yield oxygenate products up 39% turnover number 1780 for 1 h....
A series of 2,2':6',2''-terpyridine (terpy), 2,6-di(thiazol-2-yl)pyridine (dtpy) and 2,6-di(pyrazin-2-yl)pyridine (dppy) derivatives with n-quinolyl substituents (n = 2 4) was used to synthesize five-coordinate complexes [CuCl2(n-quinolyl-terpy)] (1-2), [CuCl2(n-quinolyl-dtpy)] (3-4) [CuCl2(n-quinolyl-dppy)] (5-6), respectively. The main emphasis the research investigate impact triimine skeleton (terpy, dtpy dppy) pendant substituent on antiproliferative catalytic properties 1-6. obtained...
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.
A new monoiminoacenaphthenone 3,5-(CF3)2C6H3-mian (complex 2) was synthesized and further exploited, along with the already known dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl2(dpp-mian)(CH3CN)] (3) [VOCl(3,5-(CF3)2C6H3-bian)(H2O)][VOCl3(3,5-(CF3)2C6H3-bian)]·2.85DME (4) from [VOCl2(CH3CN)2(H2O)] (1) or [VCl3(THF)3]. The structure of all compounds determined using X-ray structural analysis. vanadium atom in these structures has an octahedral coordination environment. Complex 4...
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.
The combination of a new oxidovanadium(<sc>iv</sc>) complex<bold>1</bold>with pyrazine-2-carboxylic acid (PCA; cocatalyst) affords catalytic system for the efficient oxidation saturated hydrocarbons.
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...