Search

A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and 1,2,3-triazole ring as well as nitramine group in the polymer chain have been described. The developed solvent- and catalyst-free approach is methodologically simple and effective, the comonomers used are easily available, and the resulting polymer does not need any purification. All this makes it a promising tool for the synthesis of energetic polymers. The protocol was utilized to generate multigram quantities of the target polymer, which has been comprehensively investigated. The resulting polymer was fully characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers, thermochemical characteristics, and combustion features indicate the prospects of this polymer as a binder base for energetic materials. The polymer of this study surpasses the benchmark energetic polymer, nitrocellulose (NC), in a number of properties.

Here we report the first synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (R,R)-1,2-diphenylethylenediamine and salicylaldehyde. Both diastereoisomers with opposite chiralities at the metal center (Λ and Δ configurations) were prepared. The new Co(III) complexes possessed both acidic hydrogen-bond donating (HBD) NH moieties and nucleophilic counteranions and operate as bifunctional chiral catalysts for the challenging kinetic resolution of terminal and disubstituted epoxides by the reaction with CO2 under mild conditions. The highest selectivity factor (s) of 2.8 for the trans-chalcone epoxide was achieved at low catalyst loading (2 mol %) in chlorobenzene, which is the best achieved result currently for this type of substrate.

New methylpalladium chloride complex with bulky N,N'-bis(1,2,3,4-tetrahydro-1-naphthyl)-substituted glyoxal diimine ligand was obtained. This complex was found to be an efficient catalyst for vinyl-addition polymerization of norbornene derivative and for polymerization of a diazoacetate, giving polycarbenes with side polar functionalities.

New magnetic nanomaterials based on soluble ferrocene-containing polyphenylenes were synthesized at 20–80 °C both under normal conditions and under ultrasonic irradiation. The maximum magnetization of nanomaterials containing magnetite nanoparticles was 15 G cm3 g−1 in a magnetic field of 2.5 kOe. According to transmission electron microscopy, the average statistical sizes of magnetic nanoparticles were in the range of 12–19 nm.

Here we report the first synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (

High molecular weight block terpolymers with different contents of polypropylene carbonate and cyclohexene carbonate units in the polymer chain were synthesized by the copolymerization of carbon dioxide, propylene oxide, and cyclohexene oxide. Zinc adipate was used as a catalyst. The terpolymerization products were characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, GPC, DSC, and DMA methods. The influence of the reaction conditions on the composition, microstructure, and molecular-weight and thermal characteristics was studied.

Aza-Michael reaction of ( E )-4-(diphenylphosphoryl)but-3-en-2-one with mono- and bicyclic nitrogen heterocycles proceeds regioselectively in the absence of catalysts to give the corresponding s-diphenylphosphoryl-b-azahetarylalkanones. Its reaction with imidazole in the presence of chiral organocatalysts affords the corresponding enantiomerically enriched adduct in higher yield.

The heating of the 18-electron complex [3,3-(dppb)-3-H-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (3) in benzene at 80 °C in the presence of a small amount of CCl(4) as initiator afforded paramagnetic 17-electron species [3,3-(dppb)-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (4) along with minor amounts of two P-phenylene ortho-cycloboronated derivatives [3-Cl-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (5) and [3,7-Cl(2)-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (6) in total yield of ca. 80%. The heating of either 3 or 4 in toluene at 95 °C in the absence of CCl(4) led to the selective formation of 5, which was isolated in 64% and 46% yield, respectively. Thermolysis of 3 at higher temperatures (boiling toluene, 110 °C) gives novel paramagnetic species [3-Cl-3,3,7,8-{Ph(2)P(CH(2))(4)P-μ-(C(6)H(4)-ortho)(2)}-closo-3,1,2-RuC(2)B(9)H(9)] (7) featuring bis(ortho-cycloboronation) of both P-phenyl groups at the same phosphorus atom of the ruthenium-bound dppb ligand. All new paramagnetic complexes 4-7, as well as starting diamagnetic species 3, were characterized by single-crystal X-ray diffraction and, in addition, by EPR spectroscopic studies of odd-electron complexes. Ruthenacarboranes 3-5 and 7 all display high efficiency as catalysts for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Complex 5 gave the best catalyst performance in terms of polydispersity; the PDI (M(w)/M(n)) of the polymer samples is as low as 1.15.

Terpolymers with different L-lactic acid contents in the poly(propylene carbonate) chain were synthesized by the terpolymerization of carbon dioxide, propylene oxide and L-lactide, catalyzed by zinc adipate. The terpolymerization products were characterized by 1 H and 13 C NMR, 2D { 1 H- 13 C} HMBC and FT-IR spectroscopy, DSC, TGA and GPC.

A facile preparative procedure was developed for the synthesis of 17-and 18-electron closo-(diphosphine)ruthenacarborane complexes. This method is based on the replacement of PPh3 ligands with bis(diphenylphosphino)alkanes Ph2P(CH2)nPPh2 (n = 2—4) in ruthenacarborane 3,3-(PPh3)2-3-Cl-3-H-closo-3,1,2-RuC2B9H11. The resulting complexes exhibit high activity in controlled radical polymerization of vinyl monomers.

Aza-Michael reaction of ( E )-4-(diphenylphosphoryl)but-3-en-2-one with mono- and bicyclic nitrogen heterocycles proceeds regioselectively in the absence of catalysts to give the corresponding s-diphenylphosphoryl-b-azahetarylalkanones. Its reaction with imidazole in the presence of chiral organocatalysts affords the corresponding enantiomerically enriched adduct in higher yield.

Racemiccloso-rhodacarboranes,vis. closo-(η3,2-C7H3-2-CR 2 1 )-1-R2-2-R3-3,1,2-RhC2B9H9 (R1=R2=R3=H; R1=H, R2=R3=Me; R1=R2=R3=Me) and (closo-2,2-(η3,2-C7H7-2-CH2)-2,1,7-RhC2B9H11), were successfully separated into enantiomers by high-performance liquid chromatography (HPLC).