Alexey N. Bilyachenko

Alkane oxidation with peroxides catalyzed by cage-like copper( ii ) silsesquioxanes

Isomeric cage-like tetracopper(II) silsesquioxane complexes [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1a), [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (1b) and binuclear complex [(PhSiO1.5)10(CuO)2(NaO0.5)2] (2) have been studied by various methods. These compounds can be considered as models of some multinuclear copper-containing enzymes. Compounds 1a and 2 are good pre-catalysts for the alkane oxygenation with hydrogen peroxide in air in an acetonitrile solution. Thus, the 1a-catalyzed reaction with cyclohexane at 60 °C gave mainly cyclohexyl hydroperoxide in 17% yield (turnover number, TON, was 190 after 230 min and initial turnover frequency, TOF, was 100 h−1). The alkyl hydroperoxide partly decomposes in the course of the reaction to afford the corresponding ketone and alcohol. The effective activation energy for the cyclohexane oxygenation catalyzed by compounds 1a and 2 is 16 ± 2 and 17 ± 2 kcal mol−1, respectively. Selectivity parameters measured in the oxidation of linear and branched alkanes and the kinetic analysis revealed that the oxidizing species in the reaction is the hydroxyl radical. The analysis of the dependence of the initial reaction rate on the initial concentration of cyclohexane led to a conclusion that hydroxyl radicals attack the cyclohexane molecules in proximity to the copper reaction centers. The oxidations of saturated hydrocarbons with tert-butylhydroperoxide (TBHP) catalyzed by complexes 1a and 2 exhibit unusual selectivity parameters which are due to the steric hindrance created by bulky silsesquioxane ligands surrounding copper reactive centers. Thus, the methylene groups in n-octane have different reactivities: the regioselectivity parameter for the oxidation with TBHP catalyzed by 1a is 1 : 10.5 : 8 : 7. Furthermore, in the oxidation of methylcyclohexane the position 2 relative to the methyl group of this substrate is noticeably less reactive than the corresponding positions 3 and 4. Finally, the oxidation of trans-1,2-dimethylcyclohexane with TBHP catalyzed by complexes 1a and 2 proceeds stereoselectively with the inversion of configuration. The 1a-catalyzed reaction of cyclohexane with H216O2 in an atmosphere of 18O2 gives cyclohexyl hydroperoxide containing up to 50% of 18O. The small amount of cyclohexanone, produced along with cyclohexyl hydroperoxide, is 18O-free and is generated apparently via a mechanism which does not include hydroxyl radicals and incorporation of molecular oxygen from the atmosphere.

Peculiarities of the Complexation of Copper and Silver Adducts of a 3, 5-Bis (trifluoromethyl) pyrazolate Ligand with Organoiron Compounds

Interaction of the copper, {[3,5-(CF(3))(2)Pz]Cu}(3), and silver, {[3,5-(CF(3))(2)Pz]Ag}(3), macrocycles [3,5-(CF(3))(2)Pz = 3,5-bis(trifluoromethyl)pyrazolate] with cyclooctatetraeneiron tricarbonyl, (cot)Fe(CO)(3), was investigated by IR and NMR spectroscopy for the first time. The formation of 1:1 complexes was observed at low temperatures in hexane. The composition of the complexes (1:1) and their thermodynamic characteristics in hexane and dichloromethane were determined. The π-electron system of (cot)Fe(CO)(3) was proven to be the sole site of coordination in solution and in the solid state. However, according to the single-crystal X-ray data, the complex has a different (2:1) composition featuring the sandwich structure. The complexes of ferrocene with copper and silver macrocycles have a columnar structure (X-ray data).

A Heterometallic (Fe6Na8) Cage-like Silsesquioxane: Synthesis, Structure, Spin Glass Behavior and High Catalytic Activity

The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO1.5)20(FeO1.5)6(NaO0.5)8(n-BuOH)9.6(C7H8)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation. The magnetic property investigations revealed that it shows an unusual spin glass-like behavior induced by a particular triangular arrangement of Fe(III) ions. Cyclohexane and other alkanes as well as benzene can be oxidized to the corresponding alkyl hydroperoxides and phenol, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex I and nitric acid. The I-catalyzed reaction of cyclohexane, c-C6H12, with H216O2 in an atmosphere of 18O2 gave a mixture of labeled and non-labeled cyclohexyl hydroperoxides, c-C6H11–16O–16OH and c-C6H11–18O–18OH, respectively, with an 18O incorporation level of ca. 12%. Compound I also revealed high efficiency in the oxidative amidation of alcohols into amides: in the presence of complex I, only 500 ppm of iron was allowed to reach TON and TOF values of 1660 and 92 h−1.

Heterometallic Na6Co3 Phenylsilsesquioxane Exhibiting Slow Dynamic Behavior in its Magnetization

A heterometallic phenylsilsesquioxane [(PhSiO1,5)22(CoO)3(NaO0.5)6]⋅(EtOH)6⋅(H2O) 1 cage architecture of Co(II) ions in a triangular topology exhibits a slow dynamic behavior in its magnetization, induced by the freezing of the spins of individual molecules.

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

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 and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides

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%, and 16% yields, respectively. Nuclearity and structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product 1 is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on two condensed pentamembered siloxane cycles. Topological analysis of metal clusters in products 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydroperoxide TBHP to ketones or alkanes with H2O2 to alkyl hydroperoxides in acetonitrile.

Cage-like Fe,Na-Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe6 O19 } core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]5 . This structural organization induces antiferromagnetic interactions between the FeIII ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.

Ionic Complexes of Tetra- and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

Herein, we describe an approach to cage metallasilsesquioxanes by self‐assembly with 1,2‐bis(diphenylphosphino)ethane as a key reactant. This approach allowed us to achieve a unique family of complexes that includes anionic tetra‐ and nonanuclear cage copper(II) sodium silsesquioxane and cationic copper(I) 1,2‐bis(diphenylphosphino)ethane components. Additional representatives of this intriguing metallasilsesquioxane family (Cu9Na6 and Cu9Na3Cs3) were obtained through the replacement of the original ethanol‐based reaction medium by DMSO. The fascinating structural peculiarities of all products were established by using XRD and topological studies. Initial tests for the application of the synthesized complexes as catalysts revealed their very high activity in the homogeneous oxidation of alkanes and alcohols to produce alkyl hydroperoxides, ketones, and amides.

Family of Polynuclear Nickel Cagelike Phenylsilsesquioxanes; Features of Periodic Networks and Magnetic Properties

A new family of bi-, tetra-, penta-, and hexanickel cagelike phenylsilsesquioxanes 1-6 was obtained by self-assembly and transmetalation procedures. Their crystal structures were established by single-crystal X-ray analysis, and features of crystal packing relevant to the network formation were studied by a topological analysis. Compounds 1, 2, and 4 are isolated architectures, while 3, 5, and 6 present extended 1D and 3D networks. The investigation of magnetic properties revealed the presence of ferro- (1 and 3-5) or antiferromagnetic (2 and 6) interactions between Ni(II) ions, giving rise in the most cases (1, 2, and 4-6) to the presence of a slow relaxation of the magnetization, which can originate from the spin frustration.

Quantum chemical study of the template synthesis of cage-like metallasiloxanes

The template synthesis of cage-like metallasiloxanes from oligomeric metallasiloxanes and alkaline metal silanolates was simulated by the DFT/B3PW91/6–31g(d,p) quantum chemical calculation using the Gaussian 09 program. Three possible directions of the reaction were considered. The structural parameters of the formed compounds were compared to the experimental results. The enthalpies of the processes in different solvents were estimated. The possibility of the transition of solvate molecules in the course of the synthesis from the transition metal ion to the alkaline metal ion was shown. The factors governing the formation of six-membered coordination cycles as the main structural units of arising cage-like metallasiloxanes were revealed.