Group ib organometallic chemistry : XXXIV. Thermal behaviour and chemical reactivity of tetranuclear Me2N-substituted diarypropenylcopper-copper anion (Vi2Cu4X2) and mixed diarylpropenyl/organocopper (Vi2Cu4R2) compounds

Thermal decomposition of configurationally pure 1,2-diarylpropenylcopper compounds Z-Vi₂CU₄Br₂ and Z-Vi₂Cu₄R₂ [Vi  (2-Me₂NC₆H₄)CC(Me)-(C₆H₄Me-4), R  2-Me₂NC₆H₄ or 4-MeC₆H₄CC] predominantly results in the formation of ViH. In contrast, only dimers (ViVi) were formed on thermolysis of (Z-ViCu₂OTf)_η which is a further illustration of the influence of the counter anion on the reactivity of organocopper cluster compounds. However, in both cases partial inversion of configuration, giving mixtures of isomers, was observed. The thermolysis of (Z-ViCu₂OTf)_η is discussed in terms of OTf-enhanced intraaggregate electron-transfer processes. The formation of incipient vinyl cations which are η²-coordinated to the copper cluster can explain the observed isomerization.Also in the hydrolysis reaction of Z-Vi₂Cu₄Br₂ mixtures of isomeric ViH compounds were obtained, the E/Z ratio being dependent on the type of reagent used. Mixtures of isomeric ViX compounds (X  Br, Cl, I) were formed in the reaction of Z-Vi₂Cu₄Br₂ with I₂ and CuCl₂. An explanation for the occurrence of isomerization is presented.Dimers (ViVi) were almost absent in the product mixture resulting from the reaction of Z-Vi₂Cu₄Br₂ with CuCl₂. In contrast, ViVi is obtained in about 50% yield from the reaction of ViLi with CuCl₂ which is in accord with earlier observations for the reaction of aryllithium compounds with cupric halides.Highly selective E-ViBr formation was observed in the reaction of E-ViLi with AgBr. This reaction probably proceeds via a thermally unstable Z-ViAg₂Br intermediate.     

One-step synthesis of pentavalent triphenylantimony derivatives Ph3Sb(OSiR3)2, Ph3Sb(OCH2CH2)2NH and Ph3Sb(OCH2CH2NMe2)2: X-ray molecular structure of Ph3Sb(OSiMe3)2

Pentavalent bis(triorganosiloxy)triphenylantimony derivatives, Ph₃Sb(OSiR₃)₂ (R = Me, Ph), were synthesized by reaction of triphenylantimony with trimethyl- or triphenylsilanol in the presence of tert-butylhydroperoxide by the mild reaction conditions (0-5 °C, 2 h). The reaction of triphenylantimony with diethanolamine in the presence of tert-butylhydroperoxide gave the cyclic compound Ph₃Sb(OCH₂CH₂)₂NH. The mixture of Ph₃SbO and Ph₃Sb(OCH₂CH₂NMe₂)₂ was obtained by the reaction of triphenylantimony with 2-(N,N-dimethylamino)ethanol in the presence of tert-butylhydroperoxide.     

The production of H(2S) atoms in the energy-transfer reaction of O2(1Δg) with HO2(X̃2A″)

The reaction of O₂(¹Δg) with HO₂(X?) was studied in an isothermal flow reactor in the pressure range 7?p? 10.7 mbar at temperatures between 299?T? 423 K. H-atom production was observed in the reaction O₂(¹Δg) + HO₂(òA′) - H(²S)+ 2O₂ (³Σ_g^?). The rate of this reaction (k₁) is estimated to be k₁ = (1 ± 0.5) × 10¹⁴ CM³ Mol^?1 s^?1. The implications of this reaction to recent determinations of the rate of the reaction H + O₂(¹Δg) are discussed.     

The nickel-catalysed carbonylation of 2-mercaptoethanol

2-Mercapthoethanol undergoes carbonylation in pyridine solution in the presence of oxygen and of [Ni(CO)₃Pyl as a catalyst to give cyclic O, S-ethylelnethiorcarbonate. The isolation of thiolatonickel compound [Ni(SCH₂CH₂OH)₂] by the oxidation of a solution containing [Ni(CO)₃Py] and 2-mercaptoethanol, and its reaction with carbon monoxide to give the cyclic thiocarbonate and [Ni(CO)₃Py] prove that the reaction proceeds in at least two steps.     

Kinetics of the reactions of isopropoxy radicals with NO,NO2, and O2

A fluorescence excitation spectrum of (CH₃)₂CHO (isopropoxy radical) is reported following photolysis of isopropyl nitrite at 355 nm. Rate constants for the reaction of isopropoxy with NO, NO₂, and O₂ have been measured as a function of pressure (1–50 Torr) and temperature (25–110°C) by monitoring isopropoxy radical concentrations using laser-induced fluorescence. We have obtained the following Arrhenius expressions for the reaction of isopropoxy with NO and O₂ respectively: (1.22±0.28)×10^?11 exp[(+0.62±0.14 kcal)/RT]cm²/s and (1.51±0.70)×10^?14 exp[(?0.39±0.28)kcal/RT]cm³/s where the uncertainties represent 2σ. The results with NO₂ are more complex, but indicate that reaction with NO₂ proceeds more rapidly than with NO contrary to previous reports. The pressure dependence of the thermal decomposition of the isopropoxy radical was studied at 104 and 133°C over a 300 Torr range using nitrogen as a buffer gas. The reaction is in the fall-off region over the entire range. Upper limits for the reaction of isopropoxy with acetaldehyde, isobutane, ethylene, and trimethyl ethylene are reported.We have performed the first LIF study of the isopropoxy radical. Arrhenius parameters were measured for the reaction of i-PrO with O₂, NO, NO₂, using direct radical measurement techniques. All reactions are in their high-pressure limits at a few Torr of pressure. The rate constant for the reactions of i-PrO with NO and NO₂ reactions exhibit a small negative activation energy. Studies of the i-PrO + NO₂ reaction produce data which indicate that O(³P) reacts rapidly with i-PrO. Unimolecular decomposition studies of i-PrO indicate that the reaction is in the fall-off region between 1 and 300 Torr of N₂ and the high-pressure limit is above 1 atmosphere of N₂.     

Synthesis of 2-cyclopropyl-4-pyrones and 5-cyclopropyl-2-alkylene-3(2H)-furanones based on tandem cyclization-cyclopropanation strategy

In AgSbF₆/Rh₂(OAc)₄/DCE system, two-component diastereoselective reactions of 2-diazo-3,5-dioxo-6-ynoates (phosphonates and sulphones) and alkenes provided easy access to 2-cyclopropyl-γ-pyrones through 6-endo-dig cyclization-cyclopropanation. In AgOAc/Rh₂(OAc)₄/Et₃N/DCE system, two-component reaction of 2-diazo-3,5-dioxo-7-aryl-6-ynoates and alkenes afforded 2-cyclopropyl-2-alkylene-3(2H)-furanones through 5-exo-dig cyclization-cyclopropanation. The possible mechanism of reaction is discussed. A simple procedure and mild conditions are significant features of this strategy.     

Heterogeneous reaction of SO2 on TiO2 particles

The heterogeneous reaction of SO₂ on TiO₂ particles was studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The influences of the oxygen concentration, relative humidity (RH), and ultraviolet (UV) light illumination (λ ≈ 365 nm) intensity on the reaction were investigated. The main product of the heterogeneous reaction of SO₂ on TiO₂ particles was sulfate with UV illumination and sulfite without it. The production of sulfate was promoted significantly with UV illumination or water, and there was a synergistic effect when both were present. In the dry system without UV, the heterogeneous reaction of SO₂ on TiO₂ particles was found to be second-order for SO₂ and the initial uptake coefficient, γ_BET, was determined to be 1.94 × 10^?6. With UV and RH = 40%, the reaction order was first-order and the initial uptake coefficient was 1.35 × 10^?5.     

Synthesis of trans-[Re(NO)2-(Ph2PCH2CH2PPh2)2][BF4], a formal dinitrosyl complex of rhenium(-I) and its protic denitrosylation. X-Ray structure of trans-[ReF(NO)-(Ph2PCH2CH2PPh2)2][BF4]

Treatment of a THF solution of trans-[ReCl(N₂)(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) with NO, in the presence of Tl[BF₄], forms trans-[Re(NO)₂(dppe)₂][BF₄], a rare formal 20-electron d⁸-rhenium nitrosyl complex which, by reaction with HX (X = BF₄, Cl or HSO₄), gives trans-[ReF(NO)(dppe)₂][BF₄] (2) (the X-ray structure of which is reported) or trans-[ReX(NO)(dppe)₂]X (3, X = Cl or HSO₄), respectively, as well as nitrous oxide.     

A 3D Ba-MOF for selective adsorption of CO_2/CH_4 and CO_2/N_2

An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N'-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide) and Ba(NO_3)_2,and a novel porous Ba-MOF,[H_2 N(CH_3)_2]_(0.5) [Ba_(1.5)(L)(DMA)]·1.5 DMA·1.5 H_2 O(UPC-70,H3 L=2-(4-ca rboxy-2-methylphenyl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid,DMA=N,N-dimethylacetamide),was obtained on the basis of the partial hydrolysate.The as-synthesized 3 D network with 1 D open channels of different sizes(24 A and 10 A)contains abundant open metal sites after removal of solvents,which is conducive to the preferential adsorption of CO_2.The subsequent gas sorption measurement reveals the high separation selectivity of UPC-70 for CO_2/CH_4(15) and CO_2/N_2(32) at ambient conditions,and GCMC theoretical simulation provides good verification of the experimental results,indicating that UPC-70 is a potential candidate for CO_2 capture from flue gas and natural gas.     

Effective synthesis of novel O-acetylated compounds over ZrO2-Al2O3 solid acid

The solid acids such as ZrO₂, Al₂O₃ and ZrO₂-Al₂O₃ containing different ZrO₂ loadings (10–80 mol%) were prepared by solution combustion method (SCM) and characterized for their total surface acidity by NH₃-TPD/n-butylamine back titration method and crystallinity by powder X-ray diffraction (PXRD) technique. These solid acids were evaluated for their catalytic activity in the synthesis of novel O-acetylated products from substituted phenols, pyridine alcohols and aryl alcohols with acetic anhydride (AA) as an acetylating agent. The reaction conditions were optimized by varying the catalyst, molar ratio of the reactants, reaction temperature and amount of the catalyst. All the solid acids used in this study exhibited good catalytic activity in the reaction. In particular, ZrO₂-Al₂O₃ containing 80 mol% of ZrO₂ was found to be highly active in the acetylation reaction with high yield of acetylated products. Triangular correlation between the surface acidity, crystallinity and catalytic activity of solid acids was observed. These solid acids were found to be reactivable and reusable.     

Oxidation of 2-cyanoprop-2-enethioamides with hydrogen peroxide

Oxidation of (E)-3-aryl-2-cyanoprop-2-enethioamides with 32% H₂O₂ under mild conditions gave (E)-3-aryl-2-cyano-1-iminioprop-2-ene-1-sulfenates in 70–88% yields. Under the conditions of the Radziszewski reaction (H₂O₂, 10% aqueous KOH) or upon prolonged treatment with H₂O₂, (E)-3-aryl-2-cyanoprop-2-enethioamides underwent transformations leading to complex mixtures of oxidation products. In some cases, 3-aryloxirane-2,2-dicarboxamides were isolated from those mixtures in low yields (<20%). Treatment of 3-arylamino-2-cyanoprop-2-enethioamides with the system H₂O₂/KOH in ethanol afforded (arylaminomethylidene)malononitriles.     

Reactions of the HO2 radical with OH,H, Fe2+ and Cu2+ at elevated temperatures

The temperature dependence of the rate constant for the reactions of HO₂ with OH, H, Fe²⁺ and Cu²⁺ has been determined using pulse radiolysis technique. The following rate constants, k (dm³ mol⁻¹ s⁻¹) at 20°C and activation energies, E_a (kJ mol⁻¹) have been found. The reaction with OH was studied in the temperature range 20–296°C (k=7.0×10⁹, E_a=7.4) and the reaction with H in the temperature range 5–149°C (k=8.5×10⁹, E_a=17.5). The reaction with Fe²⁺ was studied in the temperature range 16–118°C (k=7.9×10⁵, E_a=36.8) and the reaction with Cu²⁺ in the temperature range 17–211°C (k=1.1×10⁸, E_a=14.9).     

Preparation and structural characterization of [RuCl2(CO)2{Te(CH2SiMe3)2}2] and [RuCl2(CO){Te(CH2SiMe3)2}3]

The objective of the present work was to synthesize mononuclear ruthenium complex [RuCl₂(CO)₂{Te(CH₂SiMe₃)₂}₂] (1) by the reaction of Te(CH₂SiMe₃)₂ and [RuCl₂(CO)₃]₂. However, the stoichiometric reaction affords a mixture of 1 and [RuCl₂(CO){Te(CH₂SiMe₃)₂}₃] (2). The X-ray structures show the formation of the cis(Cl), cis(C), trans(Te) isomer of 1 and the cis(Cl), mer(Te) isomer of 2. The ¹²⁵Te NMR spectra of the complexes are reported. The complex distribution depends on the initial molar ratio of the reactants. With an excess of [RuCl₂(CO)₃]₂ only 1 is formed. In addition to the stoichiometric reaction, a mixture of 1 and 2 is observed even when using an excess of Te(CH₂SiMe₃)₂. Complex 1 is, however, always the main product. In these cases the ¹²⁵Te NMR spectra of the reaction solution also indicates the presence of unreacted ligand.     

Green synthesis of 4,6-bisarylpyrimidin-2(1H)-ones and azo-linked 4-arylpyrimidin-2(1H)-ones using NiFe2O4@SiO2nPr@glucose amine as a mild nano catalyst

The clean, environmentally benign and effective synthesis of novel azo-linked 4-arylpyrimidin-2(1H)-one derivatives and 4,6-bisarylpyrimidin-2(1H)-ones via three-component reaction of various aldehydes or synthetized azo-linked aldehydes, urea, and acetophenone promoted by NiFe₂O₄@SiO₂ⁿPr@glucose amine at room temperature (25 °C) was reported. NiFe₂O₄@SiO₂ⁿPr@glucose amine were synthesized and characterized by transmission electron microscope (TEM), fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), X-ray powder diffraction (XRD) and X-ray spectroscopy (EDX). These compounds were obtained in high yields and short reaction times. The catalyst could be easily recovered and reused for six cycles with almost consistent activity. The structures of the synthesized 4,6-bisarylpyrimidin-2(1H)-one compounds were confirmed by ¹H NMR, ¹³C NMR and FTIR spectral data and elemental analyses.     

Rate of the reaction I2 + F2 → products

The rate coefficient, k1, for the reaction I2+F2k1→ products has been measured at room temperature to be k1 = (1.9 = 0.4) × 10?15 cm3/molecule s. The macroscopic rate is compared to microscopic cross-section data obtained from molecular beam experiments and is found to be consistent with the bimolecular reaction I2 + F2→ I2F + F.DG|National Research Council/Resident Research Associate.     

A study of non-isothermal kinetics of limestone decomposition in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres

The non-isothermal experiments of limestone decomposition at multi-heating rates in O₂/N₂ and O₂/CO₂ atmospheres were studied using thermogravimetry. The limestone decomposition kinetic model function, kinetic parameters of apparent activation energy (E), and pre-exponential factor (A) were evaluated by Bagchi and Malek method. The results shown that in 20 % O₂/80 % N₂ atmosphere, the limestone decomposed slowly following the contracting sphere volume model controlled by boundary reaction (spherical symmetry) in two stages, and the E increased by about 50 kJ mol^?1 in the second decomposition stage. But in 20 % O₂/80 % CO₂ atmosphere, the presence of high-concentration CO₂ significantly inhibited the limestone decomposition, and made the decomposition process occur at high temperature with a rapid rate; the decomposition kinetics was divided into three stages, the first stage was an accelerated decomposition process following the Mampel Power law model with the exponential law equation, the second stage followed the nth order chemical reaction model as an α–t deceleration process, and the third stage belonged to the random nucleation and nuclei growth model with the Avrami–Erofeev equation. And with the heating rate increasing, the reaction order n showed a slight rise tendency. The E was about 1,245 kJ mol^?1 in 20 % O₂/80 % CO₂ atmosphere, but was only about 175 kJ mol^?1 in 20 % O₂/80 % N₂ atmosphere. The E and A increased markedly in the O₂/CO₂ atmosphere.     

Rh(II)-Catalysed reactions of 2H-azirines with ethyl 2-acyl-2-diazoacetates. Synthesis of novel photochromic oxazines

Photochromic non-fused 2H-1,4-oxazines are synthesised by a Rh₂(OAc)₄-catalysed reaction of 2Н-azirines with ethyl 2-acyl-2-diazoacetates. The reaction proceeds via the formation of an azirinium ylide which undergoes ring-opening to a 2-azadiene followed by 1,6-electrocyclisation.     

Adiabatic explosion in the flash photolysis of CIFCl2H2 mixtures

Incubation period and explosive limits in the flash photolysis of a CIFCl₂H₂ mixture has been measured. The ratio of rate constants k₃₁/k₁₃ for the reversible reaction Cl+CIF α Cl₂ + F (k₁₃ is the rate constant for the forward reaction, k₃₁ for the back reaction) was measured: k₃₁/k₁₃ = 270 ? 65 (T = 295 K). Photothermal explosion theory has been generalized for the case of a chain process with the three active centers.     

Kinetics of the reaction of NH2 with NO2

The absolute rate constant of the reaction of NH₂ with NO₂ has been measured using a flash-photolysis laser resonance-fluorescence technique. The value obtained at room temperature is k₁ = 2.3 (± 0.2) × 10^?11 cm³ molecule ^?1 s^?1. A negative temperature coefficient has been found between 298 and 505 K for this reaction, k₁ = 3.8 × 10^?8 × T^?1.30 cm³ molecule^?1 s^?1. It is thought that this is the major reaction of NH₂ in the troposphere.     

Synthesis and reactions of N-acetyl- and N-(2-chloroacetyl)-N-[(2E)-1-methylbut-2-en-1-yl]-2-iodoanilines

The reaction of N-(1-methylbut-2-en-1-yl)-2-iodaniline with Ac₂O or ClCH₂C(O)Cl results in a mixture of syn- and anti-atropisomers of N-acetyl- and N-chloroacetyl-N-(1-methylbut-2-en-1-yl)-2-iodaniline in a ratio of 1:1. Ozonolysis of the latter followed by reduction with dimethyl sulfide in CH₂Cl₂ gives rise to the atropisomers mixture of 2-[N-(chloroacetyl)-N-(2-iodophenyl)]aminopropanal in a ratio of 1:3. When heated in boiling benzene, the mixture of atropoisomeric aldehydes reacts with triphenylphosphine to afford a mixture of 2-[(N-acetyl)-N-(2-iodophenyl)]aminopropanal atropisomers in 1:3 ratio.