Mechanism of the mild functionalization of arenes by diboron reagents catalyzed by iridium complexes. Intermediacy and chemistry of bipyridine-ligated iridium trisboryl complexes

This paper describes mechanistic studies on the functionalization of arenes with the diboron reagent B(2)pin(2) (bis-pinacolato diborane(4)) catalyzed by the combination of 4,4'-di-tert-butylbipyridine (dtbpy) and olefin-ligated iridium halide or olefin-ligated iridium alkoxide complexes. This work identifies the catalyst resting state as [Ir(dtbpy)(COE)(Bpin)(3)] (COE = cyclooctene, Bpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl). [Ir(dtbpy)(COE)(Bpin)(3)] was prepared by independent synthesis in high yield from [Ir(COD)(OMe)](2), dtbpy, COE, and HBpin. This complex is formed in low yield from [Ir(COD)(OMe)](2), dtbpy, COE, and B(2)pin(2). Kinetic studies show that this complex reacts with arenes after reversible dissociation of COE. An alternative mechanism in which the arene reacts with the Ir(I) complex [Ir(dtbpy)Bpin] after dissociation of COE and reductive elimination of B(2)pin(2) does not occur to a measurable extent. The reaction of [Ir(dtbpy)(COE)(Bpin)(3)] with arenes and the catalytic reaction of B(2)pin(2) with arenes catalyzed by [Ir(COD)(OMe)](2) and dtbpy occur faster with electron-poor arenes than with electron-rich arenes. However, both the stoichiometric and catalytic reactions also occur faster with the electron-rich heteroarenes thiophene and furan than with arenes, perhaps because eta(2)-heteroarene complexes are more stable than the eta(2)-arene complexes and the eta(2)-heteroarene or arene complexes are intermediates that precede oxidative addition. Kinetic studies on the catalytic reaction show that [Ir(dtbpy)(COE)(Bpin)(3)] enters the catalytic cycle by dissociation of COE, and a comparison of the kinetic isotope effects of the catalytic and stoichiometric reactions shows that the reactive intermediate [Ir(dtbpy)(Bpin)(3)] cleaves the arene C-H bond. The barriers for ligand exchange and C-H activation allow an experimental assessment of several conclusions drawn from computational work. Most generally, our results corroborate the conclusion that C-H bond cleavage is turnover-limiting, but the experimental barrier for this bond cleavage is much lower than the calculated barrier.     

Modulated differential scanning calorimetry in the glass transition region

Temperature-modulated calorimetry (TMC) allows the experimental evaluation of the kinetic parameters of the glass transition from quasi-isothermal experiments. In this paper, model calculations based on experimental data are presented for the total and reversing apparent heat capacities on heating and cooling through the glass transition region as a function of heating rate and modulation frequency for the modulated differential scanning calorimeter (MDSC). Amorphous poly(ethylene terephthalate) (PET) is used as the example polymer and a simple first-order kinetics is fitted to the data. The total heat flow carries the hysteresis information (enthalpy relaxation, thermal history) and indications of changes in modulation frequency due to the glass transition. The reversing heat flow permits the assessment of the first and higher harmonics of the apparent heat capacities. The computations are carried out by numerical integrations with up to 5000 steps. Comparisons of the calculations with experiments are possible. As one moves further from equilibrium, i.e. the liquid state, cooperative kinetics must be used to match model and experiment.On leave from Toray Industries, Inc., Otsu, Shiga 520, Japan.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U. S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. Support for instrumentation came from TA Instruments, Inc. Research support was also given by ICI Paints, and Toray Industries, Inc.     

Complex formation of poly(4-vinyl-N-alkylpyridinium) salts or polymer containing flavin mononucleotide with indole derivatives

A charge-transfer-type complex formation between poly(4-vinyl-N-propylpyridinium bromide) (C3PVP), poly(4-vinyl-N-butylpyridinium bromide) (C4PVP) or poly(4-vinyl-N-benzylpyridinium chloride) (BzPVP), and indole derivatives or between polymer containing flavin mononucleotide residues and indole derivatives was studied in the presence of simple and polyelectrolytes. The association constant (K) of the complex formation with indole acetate increased in the order BzPVP > C4PVP > C3PVP, which indicated an important contribution by hydrophobic interaction. The addition of simple and polyelectrolytes decreased the association constants. This was explained by the “secondary salt effect” of the salts. The importance of the electrostatic interactions in the complexation systems was obvious. The influence of simple electrolytes on the K values was discussed theoretically according to Manning's theory.     

STUDIES ON HUMAN LENS: I. ORIGIN AND DEVELOPMENT OF FLUORESCENT PIGMENTS

Abstract
Fluorescence spectra of normal mature human lenses have been measured and at least eight species with distinct emission characteristics identified. To determine the specific photochemical and photophysical processes responsible for the origin and development of these fluorophores, emission behavior of the products generated by successive irradiation of young human lenses (3–6 y old) as well as of L-tryptophan solution have been systematically monitored. Fluorescent products that resulted from this irradiation were comparable to many of the fluorophores detected in aged lenses, indicating that light plays a major role in the development of these pigments. In addition to photogenerated species, there are other compounds in human lenses, presumably advanced glycosylated end products, with marked fluorescence properties.
Several oxidation products of tryptophan including N -formylkynurenine or its derivatives, β-carboline or its derivatives, and anthranilic acid have been identified in the mature human lens. The development of several photoproducts also was attributed to endogenous ascorbate-mediated Maillard reaction products, which undergo photoconversion by the visible light. Although some of these chromophores could act as photosensitaizers, the sensitizing efficiency of many are low. Conversely, the near-UV filtering capability of these colored compounds conceivably could protect the vitreous and retina from development of any photochemical lesion.     

Study on methane fermentation and production of vitamin B12 from alcohol waste slurry

We studied biogas fermentation from alcohol waste fluid to evaluate the anaerobic digestion process and the production of vitamin B₁₂ as a byproduct. Anaerobic digestion using acclimated methanogens was performed using the continuously stirred tank reactor (CSTR) and fixed-bed reactor packed with rock wool as carrier material at 55°C. We also studied the effects of metal ions added to the culture broth on methane and vitamin B₁₂ formation. Vitamin B₁₂ production was 2.92 mg/L in the broth of the fixed-bed reactor, twice that of the CSTR. The optimum concentrations of trace metal ions added to the culture liquid for methane and vitamin B₁₂ production were 1.0 and 8 mL/L for the CSTR and fixed-bed reactor, respectively. Furthermore, an effective method for extracting and purifying vitamin B₁₂ from digested fluid was developed.     

Double-chelation-assisted Rh-catalyzed intermolecular hydroacylation between salicylaldehydes and 1,4-penta- or 1,5-hexadienes

Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments.     

Development of a novel potentiometric titration method for determination of polypropylene degradation

In this study, a novel potentiometric titration of hydroperoxide in degraded polypropylene (PP) is proposed. This titration is quite sensitive compared with the conventional ones such as UV and manual titrations, and its detection limit was about 2 meq/kg. The sensitivity was equal to that of molecular weight measurement by GPC for the degraded PP and, in addition, the volatilization behavior of the hydroperoxide could be detected. This titration was found to be very effective for the determination of PP degradation.     

Quantitative estimation of NH3 partial pressure in H2 desorbed from the Li-N-H system by Raman spectroscopy

The partial pressure of NH3 gas estimated by Raman spectroscopy indicates that approximately 0.1% NH3 inevitably contaminates the H2 desorbed from a hydrogen storage material composed of LiH and LiNH2 at any temperature up to 400 degrees C in a closed system.     

Semiconductor laser fluorimetry for enzyme and enzymatic assays

Near-infrared semiconductor laser fluorimetry is applied to assays of xanthine and xanthine oxidase. The fluorescence of indocyanine green in the near-infrared region is quenched by hydrogen peroxide. Xanthine is converted to uric acid by xanthine oxidase, in a reaction which also produces hydrogen peroxide; xanthine can be determined by measuring the decrease in fluorescence intensity of the dye added to the sample solution. The calibration graph for xanthine is linear from 5 × 10^?5 M to 5 × 10^?7 M. The enzyme activity can also be determined.     

A study of molecular vibrational relaxation mechanism in condensed phase based upon mixed quantum-classical molecular dynamics. I. A test of IBC model for the relaxation of a nonpolar solute in nonpolar solvent at high density

In order to investigate vibrational relaxation mechanism in condensed phase, a series of mixed quantum-classical molecular dynamics calculations have been executed for nonpolar solute in nonpolar solvent and polar solute in polar solvent. In the first paper (Paper I), relaxation mechanism of I2 in Ar, where Lennard-Jones force is predominant in the interaction, is investigated as a function of density and temperature, focusing our attention on the isolated binary collision (IBC) model. The model was originally established for the relaxation in gas phase. A key question, here, is "can we apply the IBC model to the relaxation in the high-density fluid?" Analyzing the trajectory of solvent molecule as well as its interaction with the solute, we found that collisions between them may be defined clearly even in the high-density fluid. Change of the survival probability of the vibrationally first excited state on collision was traced. The change caused by collisions with a particular solvent molecule was also traced together with the interaction between them. Each collision makes a contribution to the relaxation by a stepwise change in the probability. The analysis clearly shows that the relaxation is caused by collisions even in the high-density fluid. The difference between stepwise relaxation and the continuous one found for the total relaxation in the low-density fluid and in the high-density one, respectively, was clarified to come from just the difference in frequency of the collision. The stronger the intensity of the collision is, the greater the relaxation caused by the collision is. Further, the shorter the collision time is, the greater the resultant relaxation is. The discussion is followed by the succeeding paper (Paper II), where we report that molecular mechanism of the relaxation of a polar molecule in supercritical water is significantly different from that assumed in the IBC model despite that the density dependence of the relaxation rate showed a linear correlation with the local density of water around the solute, the linear correlation being apparently in good accordance with the IBC model. The puzzle will be solved in Paper II.