The preparation and reactivity of metal-containing monomers. 54. Thermolysis of the acrylamide monomer [Co(CH2=CHCONH2)4(H2O)2](NO3)2

The kinetics and pathways of thermolysis of the Co(II) complex with acrylamide, [Co(CH₂=CHCONH₂)₄(H₂O)₂](NO₃)₂ (1) were studied. The rate of gas evolution is satisfactorily approximated by a first-order equation of autocatalysis. The composition of gaseous and solid products of thermolysis of 1 was studied by IR spectroscopy, mass spectrometry, and electronic microscopy. Thermal transformations of acrylamide complex 1 include three macro stages: dehydration, polymerization of the dehydrated monomer, and thermooxidative destruction of the resulting polymer.     

Synthesis and reactivity of metal-containing monomers. 20. Photochemical structurization of gelatin mixtures with the participation of transition metal acrylates

The structurization activity of cobalt, nickel, and copper acrylates in gelatin layers under the influence of monochromatic laser radiation with a wavelength of 633 nm has been studied. It has been established with the aid of IR and electronic spectroscopy that the complexation of the acrylate salts of Co(II), Ni(II), and Cu(II) with gelatin is accomplished by means of the OH groups of the hydroxyproline residues. It has been shown that the photosensitivity and density of the photographic layers are determined by the nature of the transition metal and increase along the series Co(II) < Ni(II) < Cu(II). Thin phase holograms with a diffraction efficiency () equal to 33% have been obtained.Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 576–581, March, 1992.     

Preparation and reactivity of metal-containing monomers

Metal-containing monomers based on vinyl derivatives of heterocycles (4-vinylpyridine, 3,5-dimethyl-1-vinylpyrazole, 2-methyl-5-vinyltetrazole) and NiCl₂, CoCl₂, CrCl₃ have been prepared and characterized by chemical analysis, IR and electron spectroscopy. By means of spectral methods, the complex formation has been shown to involve N atom of the heterocycle, while the exocyclic C = C bond does not participate in the process. The structure of polyhedrons formed has been characterized both in the solid state and in methanol or DMF. The comparison of splitting parameters for different symmetries indicates that in passing from five-membered to six-membered vinylheterocycles, the strength of the ligand field is greatly enhanced.For part 24, seeIzv. Akad. Nauk, Ser. Khim., 1992, 2066 [Bull.Russ.Acad.Sci.Div.Chem.Sci., 1992,41, 1609].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 76–80, January, 1993.     

Preparation and reactivity of metal-containing monomers.

The thermal decomposition of Cu^II, Co^II, Ni^II, Mn^II, Fe^III, and Cr^III methacryloylacetonates has been compared with the thermal behavior of the corresponding acetylacetonates and poly (methacryioylacetonates). Dehydration and thermal polymerization of methacryioylacetonates occur at 110–160 °C. The results of the thermolysis conform with the Irving-Williams sequence for the stability of the complexes of bivalent transition metals. Thermal destruction of metallopolymers differs from that of low-molecular analogs. The temperature of complete decomposition of the compounds studied correlates with the number of electrons in the d-orbital of the metal.For part 35 seeRuss. Chem. Bull., 1993,42, 1972.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–47, January, 1994.     

Copper(II) Nitrate Complex with Acrylamide: Synthesis and Crystal Structure

The molecular structure of a copper(II) nitrate complex with acrylamide (AA), Cu(NO₃)₂· 4(CH₂=CHC(O)NH₂), was determined using X-ray diffraction analysis. The coordination of AA involves the carbonyl O atom (Cu–O 1.952–1.958 Å). The X-ray study revealed the structural features of the compound that determine its chemical properties and prevent its frontal polymerization.     

Reactivity of metal-containing monomers 66. Hydrogenation of nitrotoluene derivatives in the presence of polymer-immobilized Pd nanoparticles

A new approach to the synthesis of immobilized catalysts of the mixed type was developed: frontal polymerization of metal-containing monomers in the presence of a highly dispersed inorganic support. The synthesis of the acrylamide complex of Pd^II nitrate on the SiO₂ surface followed by polymerization and reduction results in the formation of a polymer-inorganic composite with inclusions of Pd nanoparticles stabilized by the polymer matrix on the support surface. The study of the catalytic properties in the hydrogenation of nitrotoluene derivatives showed that the polymer-immobilized Pd nanoparticles on the inorganic support are efficient catalysts for the reduction of the nitrocompounds.     

Preparation and reactivity of metal-containing monomers

Homo- and copolymerization of vanadium-containing monomers (VCM) have been studied. Radical homopolymerization of VCM is accompanied by some side reactions, such as monomer disproportionation, copolymerization with ligandin situ, cyclopolymerization, V⁵⁺V⁴⁺ reduction,etc. These reactions complicate the interpretation of the results obtained. The character of radical copolymerization of VCM with styrene or acrylonitrile is preferably radical complex. Catalytic properties of vanadium-containing homo- and copolymers (in combination with organoaluminum compounds as cocatalysts) in Ziegler-Natta ethylene polymerization have been studied. It has been shown that the products inherit the properties of immobilized polymer catalysts.For Part 39, seeIzv. Akad. Nauk, Ser. Khim., 1994, 1047 [Russ. Chem. Bull., 1994, 43, 983 (Engl. Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2139–2144, December, 1994.