Pavel V. Dorovatovskii

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.

Elucidation of the crystal structure of Coriolopsis caperata laccase: restoration of the structure and activity of the native enzyme from the T2‐depleted form by copper ions

Laccases are members of a large family of multicopper oxidases that catalyze the oxidation of a wide range of organic and inorganic substrates accompanied by the reduction of dioxygen to water. A new laccase was isolated from the basidiomycete Coriolopsis caperata strain 0677 and its amino-acid sequence was determined. According to its physicochemical properties and spectroscopic features, the laccase from C. caperata is a high redox-potential blue laccase. Attempts to crystallize the native enzyme were unsuccessful. The copper type 2-depleted (T2D) laccase was prepared and crystallized. The structure of T2D laccase from C. caperata was solved at 1.6 Å resolution, and attempts to reconstruct the T2 copper centre were performed using Cu(+) and Cu(2+) ions. The structure of T2D+Cu(+) laccase was solved at 1.89 Å resolution. It was shown that the T2D+Cu(+) laccase structure contained four copper ions in the active site. Reconstruction could not be achieved when the T2D laccase crystals were treated with CuSO4.

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.

Structure and functional studies of the ribonuclease binase Glu43Ala/Phe81Ala mutant.

Ribonuclease from Bacillus intermedius (binase) is a small basic protein with antitumour activity. The three-dimensional structure of the binase mutant form Glu43Ala/Phe81Ala was determined at 1.98 Å resolution and its functional properties, such as the kinetic parameters characterizing the hydrolysis of polyinosinic acid and cytotoxicity towards Kasumi-1 cells, were investigated. In all crystal structures of binase studied previously the characteristic dimer is present, with the active site of one subunit being blocked owing to interactions within the dimer. In contrast to this, the new mutant form is not dimeric in the crystal. The catalytic efficiency of the mutant form is increased 1.7-fold and its cytotoxic properties are enhanced compared with the wild-type enzyme.

Influence of intermolecular contacts on the structure of recombinant prolidase from Thermococcus sibiricus

Prolidases are peptidases that are specific for dipeptides with proline as the second residue. The structure of recombinant prolidase from the hyperthermophilic archaeon Thermococcus sibiricus (Tsprol) was determined at 2.6 Å resolution. The homodimer of Tsprol is characterized by a complete lack of interactions between the N- and C-terminal domains of the two subunits and hence can be considered to be the most open structure when compared with previously structurally studied prolidases. This structure exists owing to intermolecular coordination bonds between cadmium ions derived from the crystallization solution and histidine residues of a His tag and aspartate and glutamate residues, which link the dimers to each other. This linking leads to the formation of a crystal with a loose packing of protein molecules and low resistance to mechanical influence and temperature increase.

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.

First synthesis of heterocyclic allenes – benzazecine derivatives

Benzazecines with an allene fragment were prepared for the first time and in high yields via tandem reaction of 1-phenylethynyl-1-methyl(benzyl)-1,2,3,4-tetrahydroisoquinolines with activated alkynes in trifluoroethanol.

Inter­action between maleic acid and N-R-furfuryl­amines: crystal structure of 2-methyl-N-[(5-phenyl­furan-2-yl)meth­yl]propan-2-aminium (2Z)-3-carb­oxy­acrylate and N-[(5-iodo­furan-2-yl)meth­yl]-2-methyl­propan-2-aminium (2Z)-3-carb­oxy­prop-2-enoate

The molecular and crystal structures of two N-(furylmethyl)propan-2-aminium salts – the products of interaction between maleic acid and N-R-furfurylamines – were studied by X-ray diffraction and correlated with their lack of reactivity in [4 + 2] cycloaddition reactions.

Synthesis and structure of new polyhedral Ni, Na- and Cu, Na-metallasiloxanes with tolyl substituent at the silicon atom

Two new polyhedral tolyl-containing metallasiloxanes, {(Na+)2[TolSi(O)O−]6(Ni2+)4(Na+)4(OH−)2[TolSi(O)O−]6}*(EtOH)14(H2O)2 and {[CuSi(O)O−]12(Cu2+)4(Na+)4}*(EtOH)8}, and two new large stereoregular cyclosiloxanes, cis-[TolSi(O)OSiMe3]6 and tris-cis-tris-trans-[TolSi(O)OSiMe3]12, have been synthesized and their structures have been determined by X-ray crystallography.