Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Optimality of the double exponential formula – functional analysis approach –

Summary. In the light of the functional analysis theory we establish the optimality of the double exponential formula. The argument consists of the following three ingredients: (1) introduction of a number of spaces of functions analytic in a strip region about the real axis, each space being characterized by the decay rate of their elements (functions) in the neighborhood of the infinity; (2) proof of the (near-) optimality of the trapezoidal formula in each space introduced in (1) by showing the (near-) equality between an upper estimate for the error norm of the trapezoidal formula and a lower estimate for the minimum error norm of quadratures; (3) nonexistence theorem for the spaces, the characterizing decay rate of which is more rapid than the double exponential. Received September 15, 1995 / Accepted December 14, 1995     

Stable marker-particle method for the Voronoi diagram in a flow field

The Voronoi diagram in a flow field is a tessellation of water surface into regions according to the nearest island in the sense of a “boat-sail distance”, which is a mathematical model of the shortest time for a boat to move from one point to another against the flow of water. The computation of the diagram is not easy, because the equi-distance curves have singularities. To overcome the difficulty, this paper derives a new system of equations that describes the motion of a particle along the shortest path starting at a given point on the boundary of an island, and thus gives a new variant of the marker-particle method. In the proposed method, each particle can be traced independently, and hence the computation can be done stably even though the equi-distance curves have singular points.     

Gelation with N-lauroyl-L-glutamic-α,γ-dibutylamide for liquid scintillation counting of low specific activities of35S and32P

A gelling agent, N-lauroyl-L-glutamic-,-dibutylamide, was applied for liquid scintillation counting of inorganic³²P and³⁵S. The gel with toluene cocktail is transparent and rigid for a long time. Several grams of ammonium magnesium phosphate or barium sulfate can easily be measured without complicating procedures.     

Diffusion coefficient of 36Cl in silver chloride

Diffusion coefficient of 36Cl in silver chloride was revealed to be about 1 x 10(-10)-4 x 10(-11) cm2 . s-1 in the range of 400 degrees C-200 degrees C by means of radioactive tracer measurements. Activation energy for diffusion was calculated about 0.13 eV. These results were different from those obtained by Maurer and Compton.     

Hydrogen-bonded networks in organic conductors: crystal structures and electronic properties of charge-transfer salts of tetracyanoquinodimethane with 4,4'-biimidazolium having multiprotonated States

[structure: see text] Novel hydrogen-bonded charge-transfer salts of TCNQ with mono- and diprotonated 4,4'-biimidazolium were synthesized in order to demonstrate the high potential of the 4,4'-biimidazole system in a molecular conductor from the viewpoint of crystal engineering and electronic modulation. Crystal structure analyses of neutral 4,4'-biimidazole and TCNQ salts revealed the formation of two types of hydrogen-bonding modes of the 4,4'-biimidazole moiety depending on the protonated states. Neutral 4,4'-biimidazole possessed a linear chain mode of hydrogen-bonding to construct two-dimensional network. In the TCNQ salt of monoprotonated 4,4'-biimidazolium, the 4,4'-biimidazole moiety formed a dimer by a complementary mode of hydrogen-bonding. In contrast, the salt of diprotonated 4,4'-biimidazolium showed a double linear chain mode of hydrogen-bonding to construct a three-dimensional network. The formation of two types of hydrogen-bonding modes made the difference in the stacking patterns of TCNQ columns and in their transport properties. The TCNQ salt of diprotonated 4,4'-biimidazolium exhibited high electrical conductivity (sigma(rt) = 1.1 x 10(-1) S cm(-1)).     

Molecular structures of endo[4+2]π and exo[6+4]π cycloadducts via cycloaddition reaction of n-ethoxycarbonylazepine with 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone

The cycloaddition reaction of N-ethoxycarbonyl-1H-azepine with 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone gave anti-endo [4+2]π and exo [6+4]π cycloadducts. These structures were fully identified by X-ray crystallographic techniques. Mechanism for their cycloaddition reactions are also discussed.