Generation of organo-alkaline earth metal complexes from non-polar unsaturated molecules and their synthetic applications

Organomagnesium compounds, represented by the Grignard reagents, are one of the most classical yet versatile carbanion species which have widely been utilized in synthetic chemistry. These reagents are typically prepared via oxidative addition of organic halides to magnesium metals, via halogen–magnesium exchange between halo(hetero)arenes and organomagnesium reagents or via deprotonative magnesiation of prefunctionalized (hetero)arenes. On the other hand, recent studies have demonstrated that the organo-alkaline earth metal complexes including those based on heavier alkaline earth metals such as calcium, strontium and barium could be generated from readily available non-polar unsaturated molecules such as alkenes, alkynes, 1,3-enynes and arenes through unique metallation processes. Nonetheless, the resulting organo-alkaline earth metal complexes could be further functionalized with a variety of electrophiles in various reaction modes. In particular, organocalcium, strontium and barium species have shown unprecedented reactivity in the downstream functionalization, which could not be observed in the reactivity of organomagnesium complexes. This perspective will focus on the newly emerging protocols for the generation of organo-alkaline earth metal complexes from non-polar unsaturated molecules and their applications in chemical synthesis and catalysis.

In this perspective, we highlight the recent development of metallation protocols of non-polar unsaturated molecules for the generation of organo-alkaline earth metal compounds and their applications in chemical synthesis and catalysis.     

Analysis of Oversized Sliding Waveguide by Mode Matching and Multi-Mode Network Theory

Transmission and reflection coefficients of hybrid modes in the sliding waveguide are discussed on the basis of mode matching method and multi-mode network theory. It is confirmed that the decrease in power of < 0.2% at 84 GHz is obtained for 2 cm in gap of the sliding waveguide which is composed of the corrugated waveguide with 88.9 mm diam. and the smooth-wall waveguide with 110 mm diam. At the sliding length near multi-half-wavelength in vacuum, transmission and reflection powers in the sliding waveguide change slightly, because the very small amount of standing wave in high higher-mode is produced resonantly in the gap.     

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.     

Evaluating 3D position and velocity of subject in parabolic flight experiment by use of the binocular stereo vision measurement

<正>A practical method for evaluating the three-dimensional(3D) position and velocity of a moving object used in the parabolic flight experiment is developed by using the binocular stereo vision measurement theory. The camera calibration mathematic model without considering the lens distortion is introduced.The direct linear transformation(DLT) algorithm is improved to accomplish the camera calibration.The camera calibration result and optimization algorithm are used to calculate the object's world coordinate from image coordinate.The 3D position and the velocity of the moving object are obtained.The standard uncertainty in estimating the velocity is 0.0024 m/s,which corresponds to 1%level of the velocity of the object in the experiment.The results show that this method is very useful for the parabolic flight experiments.     

Noise-Robust Image Reconstruction Based on Minimizing Extended Class of Power-Divergence Measures

The problem of tomographic image reconstruction can be reduced to an optimization problem of finding unknown pixel values subject to minimizing the difference between the measured and forward projections. Iterative image reconstruction algorithms provide significant improvements over transform methods in computed tomography. In this paper, we present an extended class of power-divergence measures (PDMs), which includes a large set of distance and relative entropy measures, and propose an iterative reconstruction algorithm based on the extended PDM (EPDM) as an objective function for the optimization strategy. For this purpose, we introduce a system of nonlinear differential equations whose Lyapunov function is equivalent to the EPDM. Then, we derive an iterative formula by multiplicative discretization of the continuous-time system. Since the parameterized EPDM family includes the Kullback–Leibler divergence, the resulting iterative algorithm is a natural extension of the maximum-likelihood expectation-maximization (MLEM) method. We conducted image reconstruction experiments using noisy projection data and found that the proposed algorithm outperformed MLEM and could reconstruct high-quality images that were robust to measured noise by properly selecting parameters.     

Ultra fast melting process in femtosecond laser crystallization of thin a-Si layer

In this paper, we investigated the mechanism of crystallization induced by femtosecond laser irradiation for an amorphous Si (a-Si) thin layer on a crystalline Si (c-Si) substrate. The fundamental, SHG, THG wavelength of a Ti:Sapphire laser was used for the crystallization process. To investigate the processed areas we performed Laser Scanning Microscopy (LSM), Transmission Electron Microscopy (TEM) and Imaging Pump-Probe measurements. Except for 267 nm femtosecond laser irradiation, the crystallization occurred well. The threshold fluences for the crystallization using 800 nm and 400 nm femtosecond laser irradiations were 100 mJ/cm² and 30 mJ/cm², respectively. TEM observation revealed that the crystallization occurred by epitaxial growth from the boundary surface between the a-Si layer and c-Si substrate. The melting depths estimated by Imaging Pump-Probe measurements became shallower when the shorter wavelength was used.     

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.     

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.