A Bis(μ‐oxido)dinickel(III) Complex with a Triplet Ground State

A bis(μ‐oxido)dinickel(III) complex was synthesized and characterized by single crystal X‐ray diffraction, resonance Raman, and ESI‐mass measurements. Magnetic susceptibility measurements by SQUID and EPR spectroscopy reveal that the complex has a triplet ground state, which is unprecedented for high‐valent metal (M) complexes with [M₂(μ‐O)₂] diamond core. DFT studies indicate ferromagnetic coupling of the nickel(III) centers. The complex exhibits hydrogen abstraction reactivity and oxygenation reactivity toward external substrates.     

Catalytic degradation of polyethylene and polypropylene to fuel oil

Thermal and catalytic degradation of plastic polymers, polyethylene and polypropylene to fuel oil were carried out in batch operations. The catalysts employed were acid silica-alumina (SA-1, SA-2) and zeolite ZSM-5, and non-acidic mesoporous silica FSM (folded sheet material). The yields of product gas, liquid and residues, recovery rate of liquid products, and boiling point ranges of liquid products due to degradation were compared with those of non-catalytic thermal degradation. Both the effect of catalytic contact mode and of catalyst type on the degradation were studied. In liquid-phase degradation of PP over SA-1, liquid hydrocarbon products were obtained in a yield of 69 wt.-% with a boiling point range 36-270°C, equivalent to the boiling point of normal paraffins C6 - C15. The liquid products from catalytic degradation have a carbon-number distribution very similar to commercial motor gasoline. In vapor-phase contact, the yield of liquid products was much lower (54%) and the rate of liquid recovery was much slower. With FSM, the initial rate of degradation of PP and PE to liquid products was as fast as that over acid catalyst SA-1, but the yield of liquid products was higher. The liquid products from catalytic degradation over FSM have a carbon-number distribution similar to kerosene and diesel oil. In repeated use, SA-1 deactivated very rapidly due to coke deposition on the catalyst, whereas FSM deactivated much more slowly. These findings suggest that mesopores surrounded by the silica sheet may act as reservoir for radical species, which accelerate the degradation of plastic melt.     

Theoretical study of inverted sandwich type complexes of 4d transition metal elements: interesting similarities to and differences from 3d transition metal complexes

Inverted sandwich type complexes (ISTCs) of 4d metals, (μ-η(6):η(6)-C(6)H(6))[M(DDP)](2) (DDPH = 2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)imino}pent-2-ene; M = Y, Zr, Nb, Mo, and Tc), were investigated with density functional theory (DFT) and MRMP2 methods, where a model ligand AIP (AIPH = (Z)-1-amino-3-imino-prop-1-ene) was mainly employed. When going to Nb (group V) from Y (group III) in the periodic table, the spin multiplicity of the ground state increases in the order singlet, triplet, and quintet for M = Y, Zr, and Nb, respectively, like 3d ISTCs reported recently. This is interpreted with orbital diagram and number of d electrons. However, the spin multiplicity decreases to either singlet or triplet in ISTC of Mo (group VI) and to triplet in ISTC of Tc (group VII), where MRMP2 method is employed because the DFT method is not useful here. These spin multiplicities are much lower than the septet of ISTC of Cr and the nonet of that of Mn. When going from 3d to 4d, the position providing the maximum spin multiplicity shifts to group V from group VII. These differences arise from the size of the 4d orbital. Because of the larger size of the 4d orbital, the energy splitting between two d(δ) orbitals of M(AIP) and that between the d(δ) and d(π) orbitals are larger in the 4d complex than in the 3d complex. Thus, when occupation on the d(δ) orbital starts, the low spin state becomes ground state, which occurs at group VI. Hence, the ISTC of Nb (group V) exhibits the maximum spin multiplicity.     

Kobayashi hyperbolic imbeddings into toric varieties

Our main goal of this article is to give a characterization of an algebraic divisor on an algebraic torus whose complement is Kobayashi hyperbolically imbedded into a toric projective variety. As an application of our main theorem, we prove the following: the complement of the union of n + 1 hyperplanes in the n-dimensional projective space ${\mathbb{P}^{n}(\mathbb{C})}$ in general position and a general hypersurface of degree n in ${\mathbb{P}^n(\mathbb{C})}$ is Kobayashi hyperbolically imbedded into ${\mathbb{P}^n(\mathbb{C})}$ .     

New polymer-supported phosphonate reagents for the synthesis of Z-α,β-unsaturated esters

New polymer-supported phosphonate reagents have been prepared and evaluated for the synthesis of Z-α,β-unsaturated esters. High Z-selectivity was obtained using the reagent having two o-t-BuC₆H₄ groups.     

Organic light-emitting transistors with a thin metal layer covering a diffraction grating

We fabricated organic light-emitting transistors (OLETs) characterized by an Ag layer deposited on a one-dimensional (1D) or two-dimensional (2D) diffraction grating that acts as a combined gate insulator with SiO₂. The Ag layer was entirely covered with an organic crystal. Upon photoexcitation that crystal showed narrow linewidth emissions (NLEs) parallel to the substrate plane. The narrowed lines were either redshifted or blueshifted with rotation of the crystal around a normal to its surface with respect to the grating wave vector. Strong emissions (～10⁴–10⁶ cd m^?2) accompanied by current-injected NLEs were observed from the 1D and 2D grating OLETs.