Ruthenocene‐Type Complexes of N‐Fused Porphyrins

Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp₂] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.     

Nuclear magnetic resonance spectra of carbanions—VI. Cumyl-, α-methylbenzyl- and benzyl carbanions

The proton magnetic resonance spectra of the three title carbanions have been observed in THF with potassium as a counter ion. The ortho-protons in the α-methylbenzyl carbanion are nonequivalent at room temperature. This shows that the α-carbon in this carbanion is in the near-sp² configuration. The aromatic proton chemical shifts of the benzylpotassium obtained here are at higher shielding than those of benzyllithium reported previously by Sandel and Freedman. This seems to arise from the different ionic nature of the bonds between carbon and metal in the carbanions.     

[a,b]-factorization of a graph

Let a and b be integers such that 0 ? a ? b. Then a graph G is called an [a, b]-graph if a ? d_G(x) ? b for every x ? V(G), and an [a, b]-factor of a graph is defined to be its spanning subgraph F such that a ? d_F(x) ? b for every vertex x, where d_G(x) and d_F(x) denote the degrees of x in G and F, respectively. If the edges of a graph can be decomposed into [a.b]-factors then we say that the graph is [2a, 2a]-factorable. We prove the following two theorems: (i) a graph G is [2a, 2b)-factorable if and only if G is a [2am,2bm]-graph for some integer m, and (ii) every [8m + 2k, 10m + 2k]-graph is [1,2]-factorable.     

Kinetics of phase separation in polymer blends. Calculations based on nonlinear theory

Suzuki's scaling theory for transient phenomena is applied to the calculation of the kinetics of phase separation in the early-to-intermediate stage based on a nonlinear theory proposed by Langer, Bar-on, and Miller (LBM). Calculated results are compared with experimental data on light scattering from a polymer blend system. Deviations from predictions of Cahn's linearized theory in the early time range of phase separation can be explained well by the proposed method of calculation. Nonlinear effects are found to play an essential role in characterizing the light scattering behavior of phase separation in the intermediate stage. Time evolutions of the single-point distribution function of composition are calculated, and the results are in good agreement with those reported in digital imaging analysis experiments and computer simulations of the time-dependent Ginzburg-Landau equation. The influence of asymmetry of free-energy on the single-point distribution function is also investigated in this study. © 1993 John Wiley & Sons, Inc.     

Spatial profile measurement of electron number densities and analyte line intensities in an inductively coupled plasma

A versatile instrument for spatial profile measurement has been developed and applied to the measurement of electron number densities and analyte emission intensities in an inductively coupled plasma (ICP). A precise Y-Z stage on which the ICP source was mounted was set on a rail-based optical bench. By translating the ICP source with a precision of ± 0.01 mm, the H_β Stark broadening and analyte line intensities were measured with the use of a silicon intensified target (SIT) and a photomultiplier (PMT). Micro-computer assisted data acquisition allowed it to measure a large number of emission profiles in a short period. The ease of acquisition enabled to build up complete contour maps of electron number densities, Ca neutral atom (Ca I) and Ca ion (Ca II) line intensities, and intensity ratios of the Ca II and Ca I lines. The maximum electron number density was 4 × 10¹⁵ cm^?3 occurring low in the plasma and 5 mm off axis. In a contour map of the electron number densities a hollow region was found low in the plasma, and the distribution pattern looked like a deep “trench”. Along the central channel of the ICP, the peak position of Ca II emission occurred higher than that of Ca I emission, and the spatial distribution of Ca II emission was wider and taller than that of Ca I emission. It has been verified that Ca I is emitted mainly at the region where the electron number density is less than 1 × 10¹⁴ cm^?3.     

Almost-regular factorization of graphs

For integers a and b, 0 ? a ? a ? b, an [a, b]-graph G satisties a ? deg(x, G) ? b for every vertex x of G, and an [a, b]-factor is a spanning subgraph F such that a ? deg(x, F) ? b for every vertex x of F. An [a, b]-factor is almost-regular if b = a + 1. A graph is [a, b]-factorable if its edges can be decomposed into [a, b]-factors. When both K and t are positive integers and s is a nonnegative integer, we prove that every [(12K + 2)t + 2ks, (12k + 4)t + 2ks]-graph is [2k,2k + 1]-factorable. As its corollary, we prove that every [r.r + 1]-graph with r ? 12k² + 2k is [2k + 1]-factorable, which is a partial extension of the two results, one by Thomassen and the other by Era.     

A new synthetic method for α-ketosilanes employing methoxy(phenylthio)trialkylsilylmethane as an α-silylacyl anion equivalent

Development of a new synthetic method for α-ketosilanes can be achieved by a sequence of alkylation of methoxy(phenylthio)trialkylsilylmethane and oxidation with NaIO₄.