Theoretical studies on the imine germylenoid HNGeNaF and its insertion reaction with R-H (R = F, OH, NH2, CH3)

The geometries and isomerization of the imine germylenoid HNGeNaF as well as its insertion reactions with R-H (R = F, OH, NH₂, CH₃) have been systematically investigated at the B3LYP/6-311+G^∗ level of theory. The potential barriers of the four insertion reactions are 117.2, 172.6, 219.7, and 322.3 kJ/mol, respectively. Here, all the mechanisms of the four reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted germylene (HNGeHR) and NaF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the four reactions are 185.0, 208.1, 224.4, and 266.9 kJ/mol, respectively, which are linearly correlated with the calculated barrier heights. Compared with the insertion reaction of HNGe: and R-H, the introduction of NaF makes the insertion reaction occur easily though it is more difficult to proceed than that of insertion reaction between H₂GeNaF and R-H. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the four insertion reactions should be as follows: H-F > H-OH > H-NH₂ > H-CH₃.     

Equilibrium study of ternary complexes involving heteroaromaticN-bases and acetohydroxamic acid

Summary Stability constants (K _MAL ^MA ) and other thermodynamic parameters, including statistical factors relating to the ternary complexes (MAL) [M=Co^II, Ni^II, Cu^II or Zn^II; A=2, 2-dipyridylamine (A³), 5-nitro-o-phenanthroline (A⁵), 5-methyl-o-phenanthroline (A⁶); LH=acetohydroxamic acid] have been determined at 25° C, at ionic strength 0.1 M KNO₃. The results are compared with data on aminopolycarboxylic acids, such as iminodiacetic acid (A¹), and other unsubstituted heteroaromaticN-bases:e.g. 2, 2-bipyridine (A²),o-phenanthroline (A⁴). The resulting stability sequence is: , and for heteroaromaticN-bases: . The results have been explained in the light of electrostatic interactions, -acidities of the primary ligands (A) andcistrans equilibria for MAL.     

Methyl-and tert-butyl-substituted hydroquinones and semiquinone radicals: Bond strength estimates, enthalpy of formation, and the rate constants of their reactions with peroxy radicals

The strength of the O-H bonds (D) in hydroquinone (HQH) and its alkyl derivatives has been estimated by the intersecting parabolas method using rate constants known for the reactions of these compounds with the styrene peroxy radical. For unsubstituted HQH, D = 352.6 kJ/mol; for substituted HQH derivatives, D = 349.9 (Me), 346.9 (2,5-Me₂), 343.0 (Me₃), 347.6 (CMe₃), and 340.2 (2,5-(CMe₃)₂) kJ/mol. The enthalpies of formation of these HQH derivatives have been calculated. The O-H bond strengths in the semiquinone radicals (HQ^.) resulting from the above HQH derivatives have been calculated using a thermochemical equation to be $D_{HQ^. } $ = 236.7, 237.4, 239.8, 244.7, 240.1, and 247.5 kJ/mol, respectively. Rate constants have been determined for the reactions of the hydroquinones with tertiary and secondary peroxy radicals and HOO^. at 323 K. The rate constants of the reactions between HOO^. and benzoquinones and the relative reactivities of the HQ^. radicals in their reactions with ROO^. have been estimated.     

Coordination chemistry of trivalent and pentavalent organoarsenic heterocyclic dithiocarbamate derivatives: synthesis and characterization

A series of diphenylarsenic(III) and triphenylarsenic(V) derivatives of heterocyclic dithiocarbamates of the type: and [where X = >?CH₂ (Pipdtc), >CH–CH₃ (4-MePipdtc), >O (Morphdtc), >N-CH₃ (N-MePzdtc), and?>?NH (Pzdtc)] [n?=?1 or 2] have been synthesized by reactions of diphenylarsenic(III) chloride and triphenylarsenic(V) dibromide with the sodium salt of heterocyclic dithiocarbamates in 1?:?1 and 1?:?2?M ratios, respectively, in refluxing benzene. All these newly synthesized compounds have been characterized by their elemental analyses, molecular weight measurements, and ESI mass studies. Structures of the compounds have been proposed on the basis of IR, ¹H, and ¹³C NMR spectral data which suggest anisobidentate mode of bonding.     

Biodegradation of aromatic compounds by the yeast-like fungus Trichosporon cutaneum

The biodegradation reactions of veratryl- and guaiacylpropane compounds modeling structural fragments of the lignin macromolecule by the yeast-like fungusTrichosporon cutaneum D-46 have been investigated. It has been shown that the enzyme complex ofT. cutaneum is capable of catalyzing a series of reactions of the biotransformation of arylpropane substrates, namely: oxidation, the cleavage of the C-C bond of the propane chain, demethylation, and decarboxylation. The action of the enzymes was shown most actively in the case of substrates having an unsubstituted phenolic hydroxy group.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk. Institute of Microbiology, Belorussian Academy of Sciences, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 558–564, September–October, 1992.     

Triterpene glycosides of Thalictrum squarrosum. III. Structures of squarrogenins 1 and 2

Two genins — squarrogenin 1 and squarrogenin 2 — have been isolated from nodding meadow rue by the hydrolysis of squarrosides A1 and A2. The compounds are epimeric at C-21 and have the following structures: 1 — (21R, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3,22-30-triol, C₃₁H₅₀O₅, mp 169–171°C (hexane-acetone), [] ₅₄₆ ²⁰ –11.06° (c 4.52; pyridine); and 2 — (21S, 22S, 23R)-21-methoxy-21,23-epoxycycloart-24-ene-3,22,30-triol, C₃₁H₅₀O₅, mp 190–193°C (hexane-acetone), [] ₅₄₆ ²⁰ +106.6° (c 0.3; pyridine). The results of¹H and¹³C NMR spectroscopy and of mass spectrometry for the new compounds are given.Irkutsk Institute of Organic Chemistry, Siberian Division of the USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 510–516, July–August, 1989.     

Theoretical approach to the problem of finding effective luminophors in the isocarbostyril series

It has been established that the main reason for the low fluorescence quantum yield of unsubstituted isocarbostyril (I) is the thermally activated intersystem crossing S T_n. The positions in the molecule at which the introduction of substituents should cause the greatest bathochromic displacement of the absorption spectra have been determined on the basis of data from quantum-chemical calculations. Lowering of the S₁ level results in a decrease in the probability of intersystem crossing and, as a consequence, in an increase in the quantum yield. A number of derivatives of I have been synthesized, and their luminescence-spectroscopic properties have been investigated. The causes of the instability of 4-hydroxy- and 4-NH₂-isocarbostyrils have been discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 4, pp. 474–479, July–August, 1988.     

Yields of light products in radiolysis of binary mixture isooctane-benzene and isooctane-hexafluoro-benzen

Radiolysis of binary mixtures isooctance-benzene and isooctane-hexafluorobenzene has been studied. The yields of light products of isooctane radiolysis, namely, G/H₂/, G/CH₄/, G/C₄H₁₀/ and G/C₄H₈/, have been determined for various electron ratios of benzene- and hexafluorobenzene. The acceptance of positive charges with benzene and of electrons with hexafluorobenzene is reponsible for deviations of radiation-chemical yields towards negative side from the additivity rule. Positive deviation of G/CH₄/, G/C₄H₁₀/ and G/C₄H₈/ yields at is attributed to indirect ionization of isooctane. Monomolecular reactions of C₈H ₁₈ ⁺ have been discussed.     

Quantitative treatment of the effect of counterions on ctab-catalyzed reactions of stabilized carbonium ions with cyanide ion

The reactions of stabilized carbonium ions of setoglaucin, methyl violet, and ethyl violet with cyanide ions are largely catalyzed by the cationic micelles of cetyltrimethylammonium bromide (CTAB) in aqueous media. Added counterions (anions in this case) have strong inhibitory effects on the CTAB-catalyzed reactions in the following order: N > NO > Br^? > Cl^? > F^? > no salt. The inhibitory effects of the counterions have been attributed to the exchange between added anions and reagent (CN^?) in the micellar media. The data have been analyzed by the model schemes, and mathematical formulations were developed. Various parameters associated with the exchange process, such as equilibrium exchange constant, number of surfactant molecules per substrate molecule, number of added anions, and a factor related to the binding of additives to the catalytic micellar aggregates, have been evaluated.     

Photo-induced disproportionation of iodomalonic acid

The stoichiometry, equilibrium, and kinetics of the photo-induced disproportionation of iodomalonic acid to I^?, I₂, and tartronic acid have been studied by means of spectrophotometry and iodide selective electrode at 20.0 ± 0.2°C, pH 2.0–4.0. At pH > 2.9, only I^? and HOCH(COOH)₂ are detected as major products and the reaction reaches 100% conversion. At pH < 2.9, I₂ and malonic acid are also formed and the reaction stops at a conversion rate less than 100%. Both UV (band with a peak at 360 nm) and visible light (480 nm) have been found to be effective. Two primary photochemical processes are identified: While both reactions are sensitive to UV light, only (M2) can be affected by visible light. (M1) and (M2) are considered to initiate a chain reaction sequence in which I^· radicals oxidize iodomalonic acid. Dual effects of reaction products on the reaction rate have been observed: while iodine increases the efficiency of visible light and accelerates the reaction, malonic acid inhibits the photo-decomposition by mediating the recombination of I^· radicals to I₂. © 1995 John Wiley & Sons, Inc.     

Spectrophotometric study of reactions of substituted phenols with MBTH in alkaline medium: The effect of phenol structure on the formation of analytically useful coloured products

The oxidative coupling reactions of unsubstituted phenol, 4-cresol, 2,6-xylenol and another fourteen substituted phenols with MBTH in alkaline medium containing potassium hexacyanoferrate (III) as the oxidant were examined by spectrophotometry. The maximum yield and stability of coloured species was attained at optimum pH 9.0±0.5. Stoichiometry of the reactions involving a four-electron transfer was confirmed. The coloured products were stable in an aqueous alkaline medium containing 50% (V/V) of a water-miscible organic solvent and they could be quantitatively extracted into chloroform. Absorption maxima _max of the reaction products ranged between 495 nm and 610 nm depending on the phenol structure and their molar absorptivities fell within the range 2,500–47,000L mol^–1 cm^–1 in aq. 50% ethanol. The calibration graphs were rectilinear for 2 to 20 M phenol or 2,6-xylenol (r = 0.9994–0.9997; n = 6) and the RSD values were 1.8% (n=10) when determining 10 mol L^–1 of the analytes. The reactivity of the phenols with MBTH (and hence the yield of the coloured species in alkaline medium) depending on the analyte structure decreased in the order: 2,6-dialkylphenols or 4-halogenated 2,6-dialkylphenols>2-alkyl, 2-alkoxy or 2-arylphenols and l-naphthol>unsubstituted phenol or 2-naphthol2-halogenated phenols>4-alkylphenols and 4-halogenated phenols>2-nitrophenol>2,4-or 3,4-dialkylphenols. For some 4-halogenated phenols the elimination of halogen upon coupling with the MBTH was observed.     

Calorimetric determination of thermodynamic quantities for chemical reactions in the system CO2−NaOH−H2O from 225 to 325°C

The phase equilibrium CO₂(g)=CO₂(aq) and the aqueous reactions CO ₃ ^2– +H⁺=HCO ₃ ^– , HCO ₃ ^– +H⁺=CO₂(aq)+H₂O, and Na⁺+CO ₃ ^2– =NaCO ₃ ^– were studied from 225 to 325°C using a flow calorimetric technique. Heats of mixing of gaseous CO₂ with liquid H₂O and with aqueous NaOH solutions were measured at these temperatures. Log K, H, S, and C_p values were determined for these reactions from the heat of mixing data. Equations for these thermodynamic quantities valid at infinite dilution (I=0) and 12.4 MPa are given as a function of temperature from 225 to 325°C. The log K and H values agree well with literature values at these temperatures for the first and third reactions, but not for the second reaction. No previous results have been reported for the fourth reaction at high temperatures. The isocoulombic reaction principle is tested using the log K values determined in this study. This principle is found to be valid for the reactions where each charge on one side of the equation is balanced on the other side by a charge of the same sign and magnitude, but not for the reaction where two single negative charges (HCO ₃ ^– and OH^–) are balanced by one double negative charge (CO ₃ ^2– ).Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.Taken in part from the Ph.D. Dissertation of X. Chen, Brigham Young University, 1991.     

Spectrophotometric determination of palladium with 4-(2-pyridylazo)-resorcinol (PAR)

Summary A spectrophotometric method for the determination of palladium is described using 4-(2-pyridylazo)-resorcinol as reagent. The method involves the formation of two red coloured chelates of palladium-PAR at p_H 4.0 and 10.5 respectively. The colour reactions have sensitivity of 0.0085g cm^–2 and 0.0071g cm^–2 for logI ₀/I= 0.001. The effects of p_H, time, order of addition of reagents, temperature etc. have been investigated. The composition of the complexes (metalreagent) have been confirmed by two methods as 11 (at p_H 4.0) and 32 (at p_H 10.5).

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Zusammenfassung Eine spektrophotometrische Methode zur Palladiumbestimmung mit PAR [4-(2-Pyridylazo)-resorcin] wurde beschrieben. Zwei rotgefärbte Chelate werden bei p_H 4,0 bzw. 10,5 gebildet. Die Empfindlichkeit der beiden Reaktionen beträgt 0,0085 bzw. 0,0071g · cm^–2. Der Einfluß von p_H, Zeit, Reihenfolge der Reagenzien, Temperatur usw. wurde untersucht. Die Zusammensetzung der Komplexe entspricht dem Molverhältnis Pd: Reagens= =11 bei p_H 4,0 bzw. 32 bei p_H 10,5.

     

Radiation induced electron exchange reaction of thallium/I/-thallium/III/ at low sulfate ion concentration in perchloric acid solution

To understand the behaviour of Tl/II/ and the bridging group SO ₄ ^2– in radiation induced electron exchange reactions we have investigated the rate constants and mechanisms of reaction of Tl/II/ with Tl/I/ and Tl/III/ in perchloric acid solutions. The results indicated that Tl/II/ is an intermediate in the -ray induced electron exchange process of T1/I/–T1/III/. Sulfate ions at [SO ₄ ^2– ]>-0.02M serve as bridging groups and play an important role in accelerating the T1/II/–T1/I/ reaction. A cooperative effect was found between hydrogen peroxide and sulfate ion at low sulfate ion concentration, [SO ₄ ^2– ]0.02M in perchloric acid solution.     

Trinuclear copper(I) acetylide complexes bearing carbonyl moiety: Synthesis, characterization, and photophysical properties

A series of trinuclear copper(I) acetylide complexes with carbonyl moiety, [Cu₃(μ-dppm)₃(μ₃-η¹-CCC(O)R)₂](ClO₄) (R = H (1), CH₃ (2), OCH₃ (3), NH₂ (4), NEt₂ (5)) (dppm = bis(diphenylphosphino)methane), have been synthesized and characterized. The crystal structures of [Cu₃(μ-dppm)₃(μ₃-η¹-CCC(O)CH₃)₂](ClO₄) (2) and [Cu₃(μ-dppm)₃(μ₃-η¹-CCC(O)NH₂)₂](ClO₄) (4) were determined by X-ray diffraction. The photophysical properties of complexes 1−5 have been studied. Complexes 1−5 show luminescence both in the solid state and in acetonitrile solution at 298 K, and their emission energies are in the order: 5 > 4 > 3 > 2 > 1. Density function theory (DFT) calculations at the hybrid Perdew, Burke, and Ernzerhof functional (PBE1PBE) level were performed on model complex 1 to elucidate the emission origin of complexes 1−5.     

Gamma-ray induced decomposition of double nitrates of lanthanides with univalent and divalent cations

Double nitrates of Na and K having the composition 2M^INO₃·Ln^III(NO₃)₃·2H₂O(Ln^III=Pr, Nd, Sm, Eu, Gd, Tb and Dy) and of Ni and Cu with the composition 3M^II(NO₃)₂·2Ln^III(NO₃)₃·24H₂O (Ln^III=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy) have been prepared and their -radiolytic decomposition studied up to 500 kGy. G(NO ₂ ^– ) values of K double nitrates at 230 kGy follow the order Dy³⁺>Pr³⁺=Nd³⁺=Sm³⁺>Tb³⁺>Eu³⁺> Gd³⁺·G(NO ₂ ³⁺ ) for NI double nitrates are higher than those of Cu double nitrates. Variation of G(NO ₂ ^– ) with cationic radii and the number of f electrons in lanthanide ion show a minimum at Eu. Thermal decomposition studies of double nitrates were also carried out.     

Redox reactions of basic fuchsin in homogeneous aqueous media

The pulse-radiolysis technique has been employed to understand the reaction mechanism and to characterize the transient species involved in the redox processes taking place in the radiation chemistry of basic fuchsin (BF⁺). One-electron reduction and oxidation reactions of BF⁺ have been carried out in homogeneous aqueous solutions employing various reducing (e _aq ^– , (CH₃)₂COH, CO ₂ ^– ) and oxidizing (N ₃, Br, Cl ₂ ^– Br ₂ ^– ) radicals. The absorption spectra of the transients formed in the above reactions have been attributed to semi-reduced and semi-oxidized species of BF⁺, respectively. The kinetic and spectroscopic properties of these transients have been evaluated. The reaction with H and OH radicals have also been performed and compared with those of specific one-electron reducing and oxidizing radicals. These reactions have been inferred predominantly by addition to BF⁺. Protolytic equilibria involving semi-reduced species of basic fuchsin have been studied over the pH range from 2 to 10 and the pK _a has been determined to be 3.9.     

Effects of nitric oxide on the thermal decomposition of methyl nitrite: Overall kinetics and rate constants for the HNO + HNO and HNO + 2NO reactions

The effects of NO on the decomposition of CH₃ONO have been investigated in the temperature range 450–520 K at a constant pressure of 710 torr using He as buffer gas. The measured time-dependent concentration profiles of CH₃ONO, NO, N₂O, and CH₂O can be quantitatively accounted for with a general mechanism consisting of various reactions of CH₃O, HNO, and (HNO)₂. The results of kinetic modeling with sensitivity analyses indicate that the disappearance rate of CH₃ONO is weakly affected by NO addition, whereas that of the HNO intermediate strongly altered by the added NO. In the presence of low NO concentrations, the modeling of N₂O yields leads to the rate constant for the bimolecular reaction, HNO + HNO → N₂O + H₂O (25): In the presence of high NO concentrations (P_NO > 50 torr), the modeling of CH₂O yields gives the rate constant for the termolecular radical formation channel, HNO + 2NO → HN₂O + NO₂ (35): Discussion on the mechanisms for reactions (25) and (35), and the alkyl homolog of (35), RNO + 2NO, is presented herein. © John Wiley & Sons, Inc.     

Enthalpy and entropy changes for the intercalation of small molecules to DNA. I. Substituted naphthalene monoimides and naphthalene diimides

Calorimetric studies have been performed on the intercalation of a series of nitro and amino substituted naphthalene monoimide cations to calf thymus DNA. For comparison, we also included in the study the unsubstituted naphthalene diimide dication. All of the substituted naphthalene monoimides formed dimers at the concentrations used in the calorimetric titrations, and dimerization constants for these compounds were derived from spectroscopic studies and used in calculating the H _B ^o parameters from the calorimetric data. The dimerization constants increase in the order 3-NO₂MI=4-NO₂MI>3-NH₂MI>4-NH₂MI. For the unsubstituted naphthalene monoimide and 3-NO₂MI and 4-NO₂MI, the H _B ^o parameters are within experimental error equal to that found for the naphthalene diimide, i.e., –4.3 kcal-mol^–1. Thus, changes in entropy cause the K _B for the diimide to be 40 times larger than that for the monoimide. This observation is consistent with the current electrostatic theory for counterion binding to DNA: a dication should cause the release of more counterions than a monocation and produce a more positive S _B ^o . For the amino substituted naphthalene monoimides, the K _B values are similar to the other monoimides, but H _B ^o =–6.7 kcal-mol^–1. We propose that a hydrogen bond is responsible for the unusual enthalpy and entropy effects seen for 3-NH₂MI and 4-NH₂MI.