Thermolysis Of Compounds Research Articles

Adjusting the Number of Functional Groups in Vicinal Bis(trichlorosilylated) Benzenes.

Organo(chloro)silanes are essential chemicals, but the synthesis of compounds of the formula RnSiCl4‒n with defined values of n is usually laborious. Herein, we first disclose that a [4+2]-cycloaddition between readily available Cl3SiC≡CSiCl3 and selected dienes provides facile access to vicinal bis(trichlorosilylated) benzenes and bicyclo[2.2.2]octa-2,5-dienes. Second, we show how the number of six Si‒Cl bonds in 1,2-(Cl3Si)2C6H2Me2 (1) can be selectively reduced to four or two by reaction with pinacol (H2pin) or catechol (H2cat), which act as Si···Si'-bridging and/or Si-chelating ligands. Third, we demonstrate that the thermolysis of compound 6, which contains a benzannulated eight-membered C2(SiCl2)2(μ-pin) ring with Si···Si'-bridging pin moiety, furnishes 13 with a benzannulated five-membered C2(SiCl2)2O ring via the release of pinacolone. Such cyclic disiloxanes are valuable building blocks for specialty silicones; an alternative assembly of the Si‒O‒Si unit by controlled hydrolysis of 1 is not feasible if the four valuable Si‒Cl functionalities are to be retained for further derivatization. Substitution of one Cl atom per Si site of 13 gives the rac-1,3-disila-2-oxaindane rac-15 with high selectivity.

Formation of Catalytically Active Nanoparticles under Thermolysis of Silver Chloroplatinate(II) and Chloroplatinate(IV).

The thermal behaviour of Ag2[PtCl4] and Ag2[PtCl6] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first stage, the complexes decompose in the temperature range of 350–500 °C with the formation of platinum and silver chloride and the release of chlorine gas. At the second stage, silver chloride is sublimated in the temperature range of 700–900 °C, while metallic platinum remains in the solid phase. In contrast to the thermolysis of Ag2[PtCl6], the thermal decomposition of Ag2[PtCl4] at 350 °C is accompanied by significant heat release, which is associated with disproportionation of the initial salt to Ag2[PtCl6], silver chloride, and platinum metal. It is confirmed by DSC measurements, DFT calculations of a suggested reaction, and XRD. The thermolysis of Ag2[PtCl4] and Ag2[PtCl6] compounds is shown to occur in a hydrogen atmosphere in two poorly separable steps. The compounds are decomposed within 170–350 °C, and silver and platinum are reduced to a metallic state, while a metastable single-phase solid solution of Ag0.67Pt0.33 is formed. The catalytic activity of the resulting nanoalloy Ag0.67Pt0.33 is studied in the reaction of CO total (TOX) and preferential (PROX) oxidation. Ag0.67Pt0.33 enhanced Pt nano-powder activity in CO TOX, but was not selective in CO PROX.

Formation of Catalytically Active Nanoparticles Under Thermolysis of Silver Chloroplatinate(II) and Chloroplatinate(IV)

The thermal behaviour of Ag2[PtCl4] and Ag2[PtCl6] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first stage, the complexes decompose in the temperature range of 350-500°C with the formation of platinum and silver chloride and the release of chlorine gas. At the second stage, silver chloride is sublimated in the temperature range of 700-900 °C, while metallic platinum remains in the solid phase. In contrast to the thermolysis of Ag2[PtCl6], the thermal decomposition of Ag2[PtCl4] at 350 °C is accompanied by significant heat release, which is associated with disproportionation of the initial salt to Ag2[PtCl6], silver chloride, and platinum metal. It is confirmed by DSC measurements, DFT calculations of a suggested reaction, and XRD. The thermolysis of Ag2[PtCl6] and Ag2[PtCl6] compounds is established to occur in a hydrogen atmosphere in two poorly separable steps. The compounds are decomposed within 170-350°C, and silver and platinum are reduced to a metallic state, while a metastable single-phase solid solution of Ag0.67Pt0.33 is formed. The catalytic activity of the resulting nanoalloy Ag0.67Pt0.33 is studied in the reaction of CO total (TOX) and preferential (PROX) oxidation. Ag0.67Pt0.33 advanced Pt nanopowder in activity in CO TOX, but was not selective in CO PROX.

Convenient Route to Heterometallic Group 4-Zinc Precursors for Binary Oxide Nanomaterials.

In this study, simple and efficient synthetic routes to a family of uncommon group 4-zinc heterometallic alkoxides were developed. Single-source molecular precursors with the structures [Cp2TiZn(μ,η-OR)(THF)Cl2] (1), [Zr3Zn7(μ3-O)(μ3,η2-OR)3(μ-OH)3(μ,η2-OR)6(μ,η-OR)6Cl6] (2), and [Hf3Zn7(μ3-O)(μ3,η2-OR)3(μ-OH)3(μ,η2-OR)6(μ,η-OR)6Cl6] (3) were prepared via reduction of Cp2TiCl2 with metallic zinc or protonolysis of the metal-cyclopentadienyl bond in Cp2M'Cl2 (M' = Zr or Hf) in the presence of 2-methoxyethanol (ROH) and Zn(OR)2. This synthetic route enables the creation of compounds with well-defined molecular structures and therefore provides precursors suitable for obtaining group 4-zinc oxides. Precursors 1-3 were characterized by elemental analysis, nuclear magnetic resonance and infrared spectroscopies, and single-crystal X-ray diffraction. Compound 1 decomposed at 800-900 °C to give a mixture of binary metal oxides (i.e., Zn2Ti3O8, ZnTiO3, or Zn2TiO4) and common polymorphs of TiO2 and ZnO. After calcination at 1000 °C, only TiO2 and the high-temperature-stable phase Zn2TiO4 were observed. Thermolysis of compounds 2 and 3 gave mixtures of ZnO and ZrO2 or HfO2, respectively. The obtained ZnO-ZrO2 and ZnO-HfO2 mixed oxide materials have constant phase compositions across a broad temperature range and therefore are attractive host lattices for Eu3+ for applications as yellow/red double-light-emitting phosphors. It was established that Eu3+ ions were successfully introduced into the ZnO and ZrO2/HfO2 lattices. It was revealed that Eu3+ ions prefer to occupy low-symmetry sites in ZrO2/HfO2 rather than in ZnO.

Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials.

Silicon-based moieties were anchored in heterometallic alkoxide platforms to obtain molecular clusters based on the M-O-M'-O-Si motif for the generation of mixed-metal silicate materials. Single-source molecular precursors with structures [M{(μ-ddbfo)2Al(OSiPh3)2}2], where dbbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol and M = Ba (1), Sr (2), [Sr4Ti2(μ6-O)(μ3,η2-OCH2CH2OMe)8(η-OCH2CH2OMe)2(OSiPh3)4] (3), [Sr4M'2(μ4-OH)(μ3,η2-OCH2CH2OMe)4(μ,η2-OCH2CH2OMe)6(μ-X)(OSiPh3)4] (4, with M' = Zr and X = Cl; 5 with M' = Hf and X = OH), [Sr3Hf2(μ5-O)(μ3,η2-OCH2CH2OMe)4(OCH2CH2OMe)4(OSiPh3)4] (6), and [Ca2M'2(μ3-OH)2(μ,η2-OCH2CH2OMe)4(η2-HOCH2CH2OMe)2(η-OCH2CH2OMe)2(OSiPh3)4] for M' = Zr (7), Hf (8), were prepared by substitution of methyl groups, using Ph3SiOH or chloride atoms with KOSiPh3, in [M{(μ-ddbfo)2AlMe2}2] (M = Sr, Ba) or [M4M'2(μ6-O)(μ3,η2-OCH2CH2OMe)8(OCH2CH2OMe)2(HOCH2CH2OMe)xCl4] (M = Ca, Sr, Ba, M' = Ti, Zr, Hf and x = 0, 4). The precursors were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray structural analysis. Thermal decomposition of compounds 1-8 at 1000 °C led to formation of ceramic materials that consisted of mixed-metal oxide nanocrystallites embedded in an amorphous SiO2 matrix. Compounds 1 and 2 decomposed to BaAl2Si2O8 and SrAl2Si2O8 aluminosilicates, 4 gave a mixture of SrSiO3, ZrO2, SrZrO3 and Sr7ZrSi6O21, 5 and 6 gave mixtures of various compounds, including SrHfO3, Hf0.96Si0.04O2, and SiO2, 7 lead to CaZrO3, ZrO2 and Ca3ZrSi2O9 and 8 gave a HfO2, Ca2HfSi4O12 and SiO2 phase. The thermolysis of compound 3 gave SiO2 particles of average size 40-90 nm, which contained spherical SrTiO3, SrSiO3 and Sr2TiSi2O8 nanocrystallites of diameter 5-16 nm.

Ultrasonic-assisted synthesis and the structural characterization of novel the zig-zag Cd(II) metal-organic polymer and their nanostructures

A sonochemical method was used to synthesize nano-rods of a novel cadmium(II) metal-organic coordination polymer, [Cd(p-2yeinh)(NO2)]n (1) (p-2yeinh = pyridin-2-yl ethylidene-isonicotinohydrazide). The effect of the synthesis parameters such as time, concentrations and irradiation power has been studied and optimized. It was shown that the thickness of rods has changed from 27 nm to 45 nm. The compounds were characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, X-ray powder diffraction (XPRD), and single crystal X-ray analysis. The X-ray structure analysis revealed that the Cd(II) atom is coordinated by one oxygen and three nitrogen atoms from two p-2yeinh ligands and two oxygen atoms of single nitrite anion with a CuN3O3 donor set with distorted octahedral geometry. The crystal taking the form of a one-dimensional zig-zag polymer. The adjacent chains connected by π–π of adjacent aromatic rings of p-2yeinh and other weak interactions. Consequently, the weak interactions also allow the 1D zig-zag structure to form a 3D metal-organic coordination polymer. CdO nanoparticles were prepared by thermolysis of compound 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XPRD to be 23 nm. The morphology and size of the prepared CdO nanoparticles were further studied using SEM.

ChemInform Abstract: Sequential Ketene Generation from Dioxane‐4,6‐dione‐keto‐dioxinones for the Synthesis of Terpenoid Resorcylates.

AbstractKiegiel‐type reaction of alcohols with the ketene generated in situ by thermolysis of compound (I) furnishes dioxinone‐β‐ketoesters which are transformed into the title compounds by Pd(0)‐catalyzed decarboxylative allyl migration and aromatization.

Sonochemical synthesis and characterization of three nano zinc(II) coordination polymers; Precursors for preparation of zinc(II) oxide nanoparticles

Nanostructures of three Zinc(II) coordination polymers, [Zn(NNO)2(H2O)4]n (1), [Zn(PNNO)2(H2O)2]n (2) and [Zn(H2O)6]·(INNO)2 (3) {NNO: Nicotinic acid N-oxide, PNNO: Picolinic acid N-oxide and INNO: Isonicotinic acid N-oxide}, have been synthesized by a sonochemical process and reaction of ligands with Zn(CH3COO)2. The Zinc(II) oxide nano-particles have been synthesized from thermolysis of [Zn(NNO)2(H2O)4]n (1), [Zn(PNNO)2(H2O)2]n (2) and [Zn(H2O)6]·(INNO)2 (3) at two different methods (with surfactant and without surfactant) and two temperatures (200 and 600°C). The ZnO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparison of the SEM images of ZnO nano-particles at two different methods and temperatures shows that higher temperature results in an increasing of agglomeration and thus small and spherical ZnO particles with good separation were produced by thermolysis of compounds at 200°C and by use of surfactant.

Synthesis and Characterization of ZnO Nano-rods via Thermal Decomposition of Zinc(II) Coordination Polymers and Their Photocatalytic Properties

Two Zinc(II) coordination polymers [Zn(NO2)2(3-bapp)]n·nH2O (1) and [Zn(NO2)2(4-bapp)]n·nH2O (2) have been synthesized by using zinc acetate, sodium nitrite, {3-bapp: 2,6-bis (3-amidopyridyl) pyridine} and {4-bapp: 2,6-bis (4-amidopyridyl) pyridine} as precursor. Pure phase ZnO nano-rods were obtained by thermolyses of compound 1 and 2 in 600 °C for 3 h under air atmosphere. The ZnO nano-rods were characterized by X-ray diffraction and scanning electron microscopy. The average crystallite size of ZnO nano-rods (1), (2) were determined 30 and 40 nm respectively. The particle size of hexagonal nano-rods of (1) and (2) are in the range of 20–70 and 30–80 nm respectively. The photo-catalytic performance of degradation of Congo red solution was increased when the particles size were decreased.

Synthesis and characterization of different zinc(II) oxide nano-structures from two new zinc(II)–Quinoxaline coordination polymers

Two new zinc(II) coordination polymers, [Zn(Quinoxaline)(NO3)2(H2O)2]n⋅Quinoxaline·H2O (1) and [Zn(Quinoxaline)2(Br)2]n (2), Quinoxaline=Benzopyrazine, have been synthesized and characterized by IR spectroscopy. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are one-dimensional coordination polymers with coordination environment of octahedral and tetrahedral respectively. Nanostructures of zinc(II) oxide were obtained by thermolyses of compound 1 in oleic acid, calcination of compound 1 at 500°C under air atmosphere and sol–gel processes. Also, nanopowders of zinc(II) oxide were obtained by calcination of compound 2 at 450 and 550°C. The nanomaterials were characterized by scanning electron microscopy and X-ray powder diffraction (XRD). The thermal stability of compounds 1 and 2 both their bulk were studied by thermo-gravimetric (TGA) and differential thermal analyses (DTA). This study demonstrates the coordination polymers may be suitable precursors for the preparation of nanoscale materials.

Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12]) n with unusual geometry of bismuth(III) complex anion

A reaction of freshly precipitated bismuth(III) N,N-dipropyldithiocarbamate (PDtc) with AuCl3 solution in 2 M HCl was studied. A heteropolynuclear gold(III)-bismuth complex of ionic type [Au{S2CN(C3H7)2}2]3[Bi3Cl12] (I) was isolated by crystallization of products of the heterogeneous reaction from acetone-chloroform (1: 1) solution. Crystal and supramolecular structure of compound I established by X-ray diffraction study includes structurally nonequivalent complex cations [Au{S2CN(C3H7)2}2]+ related to each other as conformers (hereinafter cations A, B, C, and D) in 1: 1: 2: 2 ratio. Due to secondary Au⋯S bonds (3.386–3.617 A), the isomeric cations form trinuclear species of two types: [C⋯A⋯C] and [D⋯B⋯D] that differ in the character of intercationic binding and Au-Au distances. Relatively weak aurophilic Au⋯Au bonds (3.4704(3) A) unite the neighboring cationic triads into zigzag polymeric chains of type (⋯[C⋯A⋯C]⋯[D⋯B⋯D]⋯)n oriented along the crystallographic axis b. The spatial isolation of neighboring chains is provided by discrete trinuclear anions [Bi3Cl12]3− where metal atoms bind four bridging (μ2 and μ3) chlorine atoms, while each bismuth atom forms distorted octahedral chromophore [BiCl6]. The complex tribismuth anion in the structure I is the first example of [Bi3Cl12]3− anion of angle rather than linear structure: Bi(1)Bi(2)Bi(3) angle is 72.358°. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal destruction includes the thermolysis of dithiocarbamate portion of the complex and [Bi3Cl12]3− accompanied by reduction of gold(III) to metal and release of BiCl3 (followed by its evaporation) and partial formation of Bi2S3. In the temperature range 680–760°C, bismuth sulfide undergoes oxidation to (BiO)2SO4, which decomposes above 760°C to give Bi2O3. Residue after thermolysis of compound I is gold metal and bismuth(III) oxide.

Synthesis, physicochemical properties, and structural isomerism of cadmium chloride coordination compounds with ɛ-caprolactam

Two new differently structured cadmium(II) coordination polymers (I and II) of the same composition Cd(Cpl)Cl2 (Cpl is ɛ-caprolactam) were synthesized. Their structure was characterized by IR spectroscopy and X-ray diffraction. Crystals of compounds I and II were monoclinic, space group P21/c, a = 10.0551(6) A, b = 15.2035(11) A, c = 6.6079(3) A, β = 108.462(2)°, V = 958.18(10) A3, ρcalcd = 2.055 g/cm3, Z = 4 for I and a = 6.66620(10) A, b = 18.9061(4) A, c = 15.5188(3) A, β = 96.8640(10)°, V = 1941.84(6) A3, ρcalcd = 2.028 g/cm3, Z = 8 for II. The thermolysis of compound I was studied thermogravimetrically.

Sodium(I)zinc(II) heteropolynuclear complex, crystal structure of a novel 2-D polymer, precursor for preparation of ZnO nanoparticles

A new coordination polymer, [Zn2Na4(CH3COO)8H2O]n (1) has been synthesized and characterized by IR spectroscopy. The single crystal X-ray data of compound 1 shows that this coordination polymer grows in two dimensions. Also, the ZnO nanoparticles has been synthesized by thermolysis of compound 1 in oleic acid, calcination at 500 and 600°C under air atmosphere and sol–gel processes. Nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of compound 1 was carried out by thermal gravimetric (TG) and differential thermal analysis (DTA). The zinc(II) oxide nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).

Synthesis and structural characterization of new two-dimensional lead(II) coordination polymer: New precursor for preparation of pure phase lead(II) oxide nanoparticles via thermal decomposition

The new lead(II) nitrate coordination polymer from ligand 2,7-bis(2-pyridyl)-3,6-diaza-2,6-octadiene (2-bpdhe), [Pb(NO3)2(2-bpdhe)]n (1) was synthesized. The compound 1 was characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The structure of 1 may be considered coordination polymer of lead(II) consisting of metallocyclic chains formed by bridging 2-bpdhe ligands, making two-dimensional array of Pb(NO3)2 and 2-bpdhe, respectively. Pure phase PbO nano-particles were obtained by thermolyses of compound 1 in oleic acid as surfactant at 180 and 200°C under air atmosphere. The PbO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).

Chemistry of Four-Membered Ring Compounds Containing a Hypervalent Sulfur Atom and a Heteroatom at the Neighbor Positions

Title compounds containing tetracoordinated and pentacoordinated sulfur together with oxygen, nitrogen, or sulfur were successfully synthesized as stable compounds. They contain the Martin ligand, which is well known to be able to stabilize such highly coordinated main group compounds. X-ray crystallographic analyses revealed that they have distorted trigonal bipyramidal (TBP) or pseudo-TBP structures. In marked contrast to group 13–15 element analogues, which afford the corresponding alkenes upon heating, thermolyses of compounds bearing an oxygen or nitrogen atom gave the corresponding oxiranes or aziridine, suggesting the possibility that these compounds are intermediates of the Corey-Chaykovsky reaction of sulfur ylides with carbonyl compounds or imines. Thermolysis of 1λ4,2-dithietanes also gave the corresponding thiiranes. The stereochemistry (retention of configuration) of formation of these three-membered ring compounds is also described.

One-dimensional Coordination Polymer as New Precursor for Preparation of Fe2O3 Nano-particles

A Fe(II) one-dimensional coordination polymer, [Fe(pyterpy)2](SCN)2.MeOH (1), which pyterpy is 4′-(4-Pyridyl)-2,2′:6′,2′-terpyridine, has been synthesized by using branched tube and characterized by elemental analysis, X-ray powder diffraction (XRD) and IR spectroscopy. Iron(III) oxide nano-particles were obtained by thermolysis of compound 1 in oleic acid (surfactant) at 286 °C under air atmosphere. The Fe2O3 nano-particles were characterized by XRD and scanning electron microscopy. This study demonstrates that the Fe(II) coordination polymers are suitable precursors for the simple one-pot preparation of iron oxide nano-materials.

Synthesis and structural characterization of new one- and two-dimensional lead(II) coordination polymers; new precursors for preparation of pure phase lead(II) oxide nanoparticles via thermal decomposition

Two new lead(II) nitrate coordination polymers from ligand 1,2-di-(4-pyridyl)-ethylene (bpe), [Pb2(μ-bpe)3(μ-NO3)2(NO3)2]n (1) and {[Pb(μ-bpe)(μ-NO3)2(NO3)(H2O)]·(Hbpe)·0.5(bpe)}n (2), were synthesized. The compounds 1 and 2 were characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The structures of 1 and 2 may be considered coordination polymers of lead(II) consisting of metallocyclic chains formed by bridging bpe ligands, making two- and one-dimensional array of Pb(NO3)2 and bpe, respectively. Pure phase PbO nano-particles were obtained by thermolyses of compounds 1–2 in oleic acid as surfactant at 180 and 200°C under air atmosphere. The PbO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).

A novel mixed-ligands holodirected two-dimensional lead(II) coordination polymer as precursor for preparation lead(II) oxide nanoparticles

A novel polymeric Pb II complex containing three different ligands, [Pb(μ-4,4′-bipy)(μ-OAc)(hfacac)] n ( 1 ) (4,4′-bipy = 4,4′-bipyridine, OAc − = acetate and hfacac − = hexafluoroacetylacetonate), has been synthesized and characterized. The single-crystal X-ray data showed that the coordination number in Pb II ion is eight with holodirected geometry. The structure may be considered as a coordination polymer of lead(II) consisting of linear double chains formed by bridging 4,4′-bipy ligands and by connecting the acetate-bridged centrosymmetric {Pb 2(OAc) 2} 2+ nodes. The self-assembly of compound 1 is likely to be caused by C–H···F–C, and π–π stacking interactions. The thermal stability of compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Nano-sized PbO was obtained by thermolyses of compound 1 in oleic acid at 290 °C under air atmosphere. The nano-materials were characterized by scanning electron microscopy, X-ray powder diffraction (XRD) and IR spectroscopy. The thermal stability of nano-structure PbO was studied by thermal gravimetric and differential thermal analyses and showed that there is no reportable loss of weight in the TGA curves that proves the existence of lead(II) oxide.

Synthesis and Characterization of ZnS and ZnO Nanoparticles via Thermal Decomposition of Two New Synthesized One-Dimensional Coordination Polymers at Two Different Temperatures

Two new Zn(II) coordination polymers from ligand 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene (bpdh) with different anions, [Zn(μ-bpdh)2(NCS)2]n (1) and [Zn(μ-bpdh)2(N3)2]n (2) were synthesized and characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The structures of the 1 and 2 may be considered coordination polymers of zinc(II) consisting of metallocyclic chains formed by bridging bpdh ligands, making a one-dimensional array of ZnII and bpdh in a 1:2 stoichiometry. Different morphologies of ZnS and ZnO nano-particles were obtained by thermolyses of compounds 1–2 in oleic acid at different temperatures under air atmosphere, respectively. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).

Thermolysis of 1-R1,R2-nitromethyl-3-R-1,2,4-triazoles

In this work thermolysis kinetics of compounds I– V was studied aiming to elucidate influence of additive substituents R1 and R2 on the rate and mechanism of decomposition reaction. maximal and initial rate is 2.0). Ratios between substance mass and reaction vessel volume (m/V = 2– 24×10 g cm) and between the vessel surface and its volume (S/V = 3.2–4.6 cm) do not affect the reaction rate constant suggesting that this reaction is homogeneous. Additives to starting material of gaseous reaction products (P0 = 106–172 mm Hg), forming during the reaction progress at 8–10% conversion, do not affect the reaction rate constant. This indicates that autocatalysis is absent in the thermolysis of compounds II–IV in the melt. The decomposition of compounds I–IV in solution and compound V in the gas phase to 45–50% conversion is described by equation of the first order reaction. The substance concentration in solution (1–5 wt %) and the dielectric constant of the solvent (6.4–20.6) have no effect on the rate constant. In the gas phase the ratio S/V was no more than 0.55 cm. The kinetic parameters of thermolysis are presented in the table. The solution concentration was 2 wt %. The measurements were performed for solutions in DOI: 10.1134/S1070363210060265