Synthesis,structures, photophysical properties,and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

The syntheses of the 2,9-dimesityl-1,10-phenanthroline ( dmesp ) metal complexes, [Cu(dmesp)(MeCN)]PF₆ ( 1 ), [Cu(dmesp)₂]PF₆ ( 2 ), Fe(dmesp)Cl₂ ( 3 ), Co(dmesp)Cl₂ ( 4 ), Ni(dmesp)Cl₂ ( 5 ), Zn(dmesp)Cl₂ ( 6 ), Pd(dmesp)MeCl ( 7 ), Cu(dmesp)Cl ( 8 ), and Pd(dmesp)₂Cl₂ ( 9 ), in good to high yields are described. These complexes were characterized by ¹H and ¹³C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1 – 8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3 – 5 , 8 , and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes ( 4 and 5 , respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively.     

Quasiclassical trajectory simulations of OH(v) + NO2 --> HONO2* --> OH(v') + NO2: capture and vibrational deactivation rate constants

Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO(2) --> HONO(2) --> OH(v') + NO(2) recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO(2) depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v') radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO(2) transient complex is approximately 90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO(2) PES, but assuming the weaker O-O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO(2). For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.     

Incorporation of fused tetrathiafulvalenes (TTFs) into polythiophene architectures: varying the electroactive dominance of the TTF species in hybrid systems

A novel polythienylenevinylene (PTV) and two new polythiophenes (PTs), featuring fused tetrathiafulvalene (TTF) units, have been prepared and characterized by ultraviolet-visible (UV-vis) and electron paramagnetic resonance (EPR) spectroelectrochemistry. All polymers undergo two sequential, reversible oxidation processes in solution. Structures in which the TTF species is directly linked to the polymer backbone (2 and 4) display redox behavior which is dictated by the fulvalene system. Once the TTF is spatially removed from the polymer chain by a nonconjugated link (polymer 3), the electroactivity of both TTF and polythiophene moieties can be detected. Computational studies confirm the delocalization of charge over both electroactive centers (TTF and PT) and the existence of a triplet dication intermediate. PTV 4 has a low band gap (1.44 eV), is soluble in common organic solvents, and is stable under ambient conditions. Organic solar cells of polymer 4:[6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) have been fabricated. Under illumination, a photovoltaic effect is observed with a power conversion efficiency of 0.13% under AM1.5 solar simulated light. The onset of photocurrent at 850 nm is consistent with the onset of the pi-pi absorption band of the polymer. Remarkably, UV-vis spectroelectrochemistry of polymer 4 reveals that the conjugated polymer chain remains unchanged during the oxidation of the polymer.     

Graft Copolymerizations of Polysaccharides. II. Acrylamide Grafting to Yellow Dextrin

Graft copolymers of acrylamide and yellow dextrin were prepared using cerium(IV) as initiator. The yellow dextrin had a very broad molecular weight distribution but was fractionated utilizing dialysis and ultrafiltration membranes. Initiator efficiencies were determined using size exclusion chromatography and were found to be between 2.4 and 34%. Initiator efficiency increased with acrylamide concentration at constant cerium (IV) and yellow dextrin concentrations, and decreased with increasing cerium(IV) concentration at constant acrylamide and yellow dextrin concentrations. Plots of acrylamide conversion and intrinsic viscosity vs initial acrylamide concentration at constant yellow dextrin and ceric ion concentrations showed a maximum at about 2.0 M.     

Organometallic Polymers. XXVII. Radical-Initiated Polymerization and Copolymerization of π-(2, 4-Hexadien-1-yl Acrylate) tricarbonyliron

The novel monomer, π-(2, 4-hexadiene- l-yl acrylate) tricarbonyliron (HATI), has been prepared by two routes. It was homopolymerized and copolymerized with acrylonitrile, vinyl acetate, styrene, and methyl acrylate in benzene solutions. In all cases azobisisobutyronitrile was the initiator. The relative reactivity ratios, where HATI is defined as M₁, were determined: r₁ = 0.34, r₂ = 0.74, M₂ = acrylonitrile; r₁ = 2.0, r₂ = 0.05, M₂ = 0.74, M₂ = acrylonitrile; r₁ = 2.0, r₂ = 0.05, M₂ = vinyl acetate; r₁ = 0.26, r₂ = 1.81, M₂ = styrene; and r₁ = 0.30, r₂ = 0.74, M₂ = methyl acrylate. The homo-and copolymers had high values of T_g. When polymerizations are carried out at high concentrations, a very high molecular weight tail is observed in HATI hompolymerizations and in HATI-methyl acrylate copolymerizations. The polymers were characterized by IR, gel permeation chromatography, viscosity, and differential scanning calorimetry studies. Finally, thermal decompositions carried out in air resulted in decomposition of the Fe(CO)₃ group, producing Fe₂O₃ as a fine powder. Thermal decomposition under nitrogen (in solution and on solids ground into KBr pellets) resulted in slow destruction of the Fe(CO)₃ groups but the resulting polymer mass was insoluble, and the question of what form the iron exists in (Fe metal, oxides, carbides, etc.) has not been answered.     

Polymerization of Methane and Olefin Mixtures over Fluosulfonic Acid and Antimony Pentafluoride

Mixtures of methane and olefins (ethylene, propylene, butenes, butadiene, and styrene) have been polymerized over HSO₃ F-SbF₃ to yield an oily oligomer with a molecular weight ranging from 100 to 700. The NMR spectra of each polymer showed a sharp peak at or near 1.25 &, suggesting the presence of block methylene in the polymer. The formation of block methylene is surprising considering the fact that the polymerization reaction is carbonium ion in nature. A primary cation has been invoked to explain the results. The formation of this primary cation must involve some extraordinary stabilization by some component in the acid.     

DIFFRACTION STUDIES OF SOME CONVENTIONAL AND NOVEL MICROPHONE BAFFLES

A directional microphone system for field recording of sounds in the air often involves a parabolic reflector to focus the sound waves on the microphone (transducer) element. Some deficiencies of such a system are noted with respect to reproduction of spectra. The reflector system, involving as it does a structure comparable to a wavelength in linear dimension, is not susceptible to traditional high- or low-frequency approximate methods of computation. Modern numerical techniques now permit precise calculation of the directional responses of small reflectors of various shapes. One result is a proposal for a very economical and effective system involving a plane reflector. Other baffle shapes are also investigated, which may be of interest in special applications.     

Recent Developments in Solid-Propellant Binders

Abstract

The complex and important role of the propellant binder in solid-propellant rockets is described. The severe weight problems of space exploratrion cause high propellant performance to be of major concern in a highly competitive field. Binders contribute to performance, not only in terms of fuel value, but by being compatible with energetic components and by providing good mechanical properties. Both sterilization required for planetary landings and compatibility problems of new energetic oxidizers generate new requirements too stringent for existing binders; only binders composed essentially of saturated aliphatic hydrocarbon are predicted to be suitable. Several saturated-binder developments are in progress. The achievements of one of these programs, based on free-radical synthesis, are evaluated against the goals of the new binder.