1-D cobalt(II) spin transition compound with strong interchain interaction: [Co(pyterpy)Cl(2)].X

Cobalt(II) compounds [Co(pyterpy)Cl(2)].MeOH (1.(MeOH)) and [Co(pyterpy)Cl(2)].2H(2)O (1.(2H(2)O)) were synthesized. The compound 1.(MeOH) forms the quasi 3-D networks by making pi-pi stacking between the 1-D chains. The methanol molecules from 1.(MeOH) can be removed by heating, and substituted by absorption of water molecules. The MeOH molecules in 1.(MeOH) are removed by heating at 410 K, and they are substituted by water molecules to form 1.(2H(2)O). 1.(2H(2)O) exhibits a S = (3)/(2) (HS) left arrow over right arrow S = (1)/(2) (LS) spin transition with a thermal hysteresis. We have succeeded in constructing a guest dependent 1-D spin-crossover cobalt(II) compound.     

Surface treatment of CaCO3 with a mixture of amino- and mercapto-functional silane coupling agents and tensile properties of the rubber composites

In order to reinforce the composite consisting of isoprene rubber (IR) and calcium carbonate (CaCO₃) particles, the surface treatment of CaCO₃ particles with a mixture of amino- and mercapto-functional silane coupling agents was investigated. The quantity of chemisorbed silanes in treated CaCO₃ measured using thermogravimetry was greater for amino- than for mercapto-silane and for the tri- than for the dialkoxy structure. Second, the molecular mobility of polycondensate of the mixtures with the trialkoxy structure measured using ¹H pulse nuclear magnetic resonance had the least molecular mobility, i.e., formed the highest density network. The greater values of stress at 500% strain, fracture stress, and elongation at break were determined for the treatment with amino- and mercapto-functional silanes having a trialkoxy structure from the stress-strain curves of composite. The mixture treatment with dialkoxy structure and with amino- or mercapto-functional silane only did not improve the mechanical properties sufficiently. Interactions between the amino group and the CaCO₃ surface, covalent bonding between the mercapto group and the IR, and high density network formation of trialkoxy silane were important for improving the mechanical properties of the composite.     

Ionization of pesticides using a far-ultraviolet femtosecond laser in gas chromatography/time-of-flight mass spectrometry

The fourth harmonic emission (200 nm) of a femtosecond Ti:sapphire laser (35 fs) was generated and used in the multiphoton ionization of 49 pesticides in gas chromatography/time-of-flight mass spectrometry. The limit of detection was improved when the ionization source from the third harmonic emission (267 nm) was replaced with the fourth harmonic emission for several pesticide molecules that contained no conjugated double bonds since their absorption bands are located in the far-ultraviolet region. This analytical instrument was used in the analysis of a series of real samples including potatoes, carrots, and cabbage, and a signal suspected to arise from di-allate was observed for the potato sample.

Application of olefin metathesis to organic synthesis. Syntheses of civetone and macrolides

Diethyl 9-octadecene-1,18-dioate was obtained in 87% yield based on 50% theoretical conversion by the olefin metathesis reaction catalyzed by WOCl₄-Cp₂TiMe₂. The Dieckmann condensation of this diester using potassium hydride afforded 2-ethoxycarbonylcyclo-9-heptadecenone, which was converted by hydrolysis and decarboxylation to cyclo-9-heptadecenone (civetone) as a mixture of cis and trans isomers (1.3 : 1) in 54% yield. Also 9-octadecen-18-olide was obtained in 17.9% by the metathesis of oleyl oleate.     

Pyrolysis of amines: Infrared spectrum of methyleneimine

Methyleneimine was detected in the gas phase by a moderately high resolution infrared spectrometer as one of the intermediate species produced by a pyrolysis of amines. Observed vibrational frequencies of some isotopic derivatives have been combined with the ab initio values to reach a most reliable force constants set. Some other spectroscopic parameters, involving geometrical parameters and dipole moment derivatives, have also been calculated ab initio and compared with the observation. Its half-life in our experimental apparatus was about 10 min, which is much longer than the previously reported values, 0.1 or 10 sec.     

Selective C−H Functionalization of Methane and Ethane by a Molecular SbV Complex

Owing to the strong nonpolar bonds involved, selective C?H functionalization of methane and ethane to esters remains a challenge for molecular homogeneous chemistry. We report that the computationally predicted main‐group p‐block Sb^V(TFA)₅ complex selectively functionalizes the C?H bonds of methane and ethane to the corresponding mono and/or diol trifluoroacetate esters at 110–180 °C with yields for ethane of up to 60 % with over 90 % selectivity. Experimental and computational studies support a unique mechanism that involves Sb^V‐mediated C?H activation followed by functionalization of a Sb^V‐alkyl intermediate.     

Preparation of calix[4]arene methylene crosslinked resins with 2-pyridyl pendant group and their adsorption behavior towards silver ion

Three different resins namely 1:5 MC-resin, 1:3 MC-resin and 1:1 MC-resin have been synthesized by methylene crosslinking of 2-pyridylcalix[4]arene. Adsorption behavior of these resins towards the metal ions existing in photographic waste was investigated. The resins show absolute efficiency for adsorption of silver ion with no affinity for other coexisting ions. First two resins form 1:1 complex whereas the third one forms 2:1 complex with silver ion. Maximum loading capacity of silver ion on the present resins was found to be 1.15, 1.29 and 0.69 mol kg^?1, respectively. Column chromatographic separation of silver ion in presence of excess of sodium ions was also carried out with 1:5 MC-resin. Selective adsorption of silver ions over excess of sodium ions was achieved.