Molecular structures and magnetic resonance spectroscopic investigations of highly distorted six-coordinate low-spin iron(III) porphyrinate complexes.

Three bis-axially ligated complexes of iron(III) octaethyltetraphenylporphyrin, (OETPP)Fe(III), have been prepared, which are low-spin complexes, each with two axial nitrogen-donor ligands (N-methylimidazole (N-MeIm), 4-(dimethylamino)pyridine (4-NMe(2)Py), and 2-methylimidazole (2-MeImH)). The crystal and molecular structure of the bis-(2-MeImH) complex shows the macrocycle to be in a saddled conformation, with the ligands in perpendicular planes aligned at 14 degrees to the porphyrin nitrogens so as to relieve the steric interaction between the 2-methyl groups and the porphyrin. The Fe-N(por) bond lengths are typical of nonplanar six-coordinate low-spin Fe(III) complexes, while the axial Fe-N(ax) bond lengths are substantially longer than those of [(TPP)Fe(2-MeImH)(2)](+) (2.09(2) A as compared to 2.015(4) and 2.010(4) A). The crystal and molecular structure of the bis-(4-NMe(2)Py) complex also shows the macrocycle to be in a mainly saddled conformation, but with a significant ruffled component. As a result, the average Fe-N(por) bonds are significantly shorter (1.951 A as compared to 1.974 A) than those of the bis-(2-MeImH) complex. One ligand is aligned at 9 degrees to two trans porphyrin nitrogens, while the other is at 79 degrees to the same porphyrin nitrogens, producing a dihedral angle of 70 degrees between the ligand planes. The EPR spectrum of this complex, like that of the bis-(2-MeImH) complex, is of the "large g(max)" type, with g(max) = 3.29 and 3.26, respectively. However, in frozen CD(2)Cl(2), [(OETPP)Fe(N-MeIm)(2)](+) exhibits both "large g(max)" and normal rhombic signals, suggesting the presence of both "perpendicular" and "parallel" ligand orientations. The 1- and 2D (1)H NMR spectra of each of these complexes, as well as the chloroiron(III) starting material, were investigated as a function of temperature. The COSY and NOESY/EXSY spectra of the chloride complex are consistent with the expected J-coupling and saddle inversion dynamics, respectively. Complete spectral assignments for the bis-(N-MeIm) and -(4-NMe(2)Py) complexes have been made using 2D (1)H NMR techniques. In each case, the number of resonances due to methylene (two) and phenyl protons (one each) is consistent with D(2)(d)() symmetry, and therefore an effective perpendicular orientation of the axial ligands on the time scale of the NMR experiments. The temperature dependences of the (1)H resonances of these complexes show significant deviations from Curie behavior, and also evidence of extensive ligand exchange and rotation. Spectral assignment of the eight methylene resonances of the bis-(2-MeImH) complex to the four ethyl groups was possible through the use of 2D (1)H NMR techniques. The complex is fluxional, even at -90 degrees C, and ROESY data suggest that the predominant process is saddle inversion accompanied by simultaneous rotation of the axial ligands. Saddle inversion becomes slow on the 2D NMR time scale as the temperature is lowered in the ligand order of N-MeIm > 4-NMe(2)Py > 2-MeImH, probably due mainly to progressive destabilization of the ground state rather than progressive stabilization of the transition state of the increasingly "hindered" bis-ligand complexes.     

Anodic stripping voltammetry of hexavalent molybdate

The anodic stripping voltammetry of hexavalent molybdate was investigated with a hanging mercury drop electrode in phosphate-borate buffer solution of pH 5.8–6.7. It was found that the deposition reaction was limited by the diffusion of the protonated molybdate ion, and the anodic stripping reaction was kinetically controlled by the dissolution of the deposited molybdate. A calibration curve for the anodic peak current versus Mo(VI) concentration was linear when Mo(VI) was within the range of 7×10^?6M and 2×10^?4M at pH 5.80. Various effects for the calibration curve were studied, and its application for the determination of Mo(VI) was discussed.     

Photochemical transformation of a dithioacetal S-oxide into the corresponding aldehyde

Irradiation of an aldehyde dithioacetal S-oxide gives the corresponding aldehyde. The mechanism of this photochemical transformation is discussed and its application to organic synthesis is also described.     

Sequence distribution of 1,4 and 3,4 units in polyisoprenes

The ¹³C-NMR spectra of hydrogenated polyisoprenes were investigated. Polyisoprenes containing various ratios of 1,4 and 3,4 units were prepared with n-BuLi/Et₂O and were hydrogenated by using p-toluenesulfonylhydrazide. ¹³C-NMR signals of the hydrogenated polymers were assigned for the triad sequences arising respectively from the 1, 4 and 3, 4 units of polyisoprenes. On the basis of these assignments it was confirmed that 1,4 and 3,4 units were randomly distributed in the polyisoprenes prepared with n-BuLi and that these polymers did not contain appreciable amounts of head-to-head or tail-to-tail 1,4 linkages.     

Rheological characterization of cross-linked poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) with various degrees of cross-linking were prepared from methyl methacrylate and a cross-linker, and the effect of dilution of the polymerizable mixture by a thermoplastic PMMA on the cross-linked PMMAs was evaluated. The rheological properties were characterized in linear viscoelasticity and in uniaxial extensional flow. A critical gel is formed at concentrations of the cross-linking agent neopentyl glycol dimethacrylate (NPG) of approximately 250 mol ppm both in the case of PMMAs, which are not diluted by an addition of thermoplastic PMMA to the monomer (Recipe-A), and of PMMAs, which were obtained by an addition of 25 wt% low molecular weight thermoplastic PMMA to the monomer (Recipe-B). Significant strain hardening is observed for concentrations of NPG at and above 100 mol ppm for PMMAs based on Recipe-A and for all PMMAs produced by Recipe-B. At the same NPG concentration of 30 mol ppm, PMMA produced by Recipe-A shows very little strain hardening, while PMMA produced by Recipe-B shows significant strain hardening. This is due to the difference in the molecular weight distribution: PMMA from Recipe-A is mono-modal with M _w /M _n = 2.5, while PMMA from Recipe-B is bimodal with M _w /M _n = 5.6. Surprisingly, the strain-hardening tendency is strongly increasing with increasing NPG concentration, and at the same NPG concentration, the strain hardening of PMMAs produced by Recipe-B is higher than that of PMMAs produced by Recipe-A. This difference can be attributed to the dilution effect of the (unreacted) thermoplastic PMMA in Recipe-B PMMAs. The elongational flow behavior was also analyzed by the Molecular Stress Function (MSF) model.     

First room temperature lasing from the fundamental state of V-grooved quantum wire lasers

Lasing from the ground state electron and heavy-hole-like transition of quantum wire (QWR) is demonstrated for the first time at room temperature, with an oxide-isolated V-grooved GaAs/AlGaAs triple QWR laser grown by flow-rate modulation epitaxy (FME). The lasing peaks at all temperatures (4–300 K) are in reasonably good agreement with both the photon energies of the peaks of the photoluminescence curves and the numerical calculation of the electronic sub-band energy states of the corresponding QWR structure. These results are considered to be responsible for the reduced heterointerface inhomogeneities (the Stokes shift 0.3 meV) of the FME grown QWR, giving a low-loss wave guide in the QWR laser.     

Palladium species in Pd/H-ZSM-5 zeolite catalysts for CH4-SCR

The active state of palladium for NO reduction with methane (CH₄-SCR) was investigated by comparing the catalytic activity of Pd/H-ZSM-5 with that of PdO/SiO₂. High catalytic activity for CH₄-SCR was given by Pd/H-ZSM-5 in the temperature range of 300–500 °C. PdO/SiO₂ catalyzed the reaction between NO₂ and CH₄ in the absence of oxygen, which retarded the reaction by consuming CH₄ in combustion. CH₄ combustion occurred on either zeolite-supported or silica-supported catalyst, while NO preferentially retarded the combustion on Pd/H-ZSM-5. NO was found to be chemisorbed on the palladium sites in zeolite, while it was hardly chemisorbed on PdO/SiO₂. NaCl titration showed that the palladium species in zeolite are Pd²⁺ cations content, on which NO is strongly chemisorbed resulting in high selectivity for CH₄-SCR.     

Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes

Improved methods for the preparation of methylene-bridged diphosphine ligands are described. Both enantiomers of the key intermediate tert-butylmethylphosphine–borane were prepared via resolution or by the conversion of one enantiomer into the opposite enantiomer. The precursor borane complexes of bis(tert-butylmethylphosphino)methane (t-Bu-MiniPHOS), bis((1,1,3,3-tetramethylbutyl)methylphosphino)methane (t-Oct-MiniPHOS), and (tert-butylmethylphosphino)(di-tert-butylphosphino)methane (trichickenfootphos) were prepared in good yields and enantiopure form.