Formation of iminophosphoranes from tetrazolopolyazines and triphenylphosphine has been studied kinetically in various solvents, and the mechanism explained as nucleophilic attack of the phosphine moiety on the trazolo ring. In the equilibrium system of tetrazolopolyazine (9) and azidopyrazine (9a) in chloroform, it is concluded that tetrazolo and azido moieties react competitively with triphenylphosphine. The mechanism of the reaction of tetrazolopolyazines with triphenylphosphine in chloroform is discussed on a phosphinium radical cation intermediate proposed. 相似文献
A series of 9,10-dihydro-9,10-(1,2-tropylio)anthracene tetrafluoroborates has been prepared. The intramolecular charge-transfer interactions in were confirmed by their UV spectra and pKR+ values. As a model compound 1,2,3,4-tetrahydro-1,4-(1,2-tropylio)naphthalene tetrafluoroborate ()_was also examined. 相似文献
Yellow and colourless complexes of molybdophosphate were investigated by the use of laser Raman spectroscopy. Two kinds of yellow molybdophosphates were identified in the weakly acidic solutions: 12-molybdophosphoric and 11-molybdophosphoric acid which are in equilibrium in solution at pH 1-2. When excess phosphate is present, the colourless molybdophosphate is formed. This complex exists in the solutions of pH 4-1 under the condition of excess phosphate ([P]/[Mo] > 2). This complex was confirmed to be P2Mo5O6?23 and is so stable that the yellow molybdophosphate is converted into the colourless by excess phosphate. 相似文献
Changes in the electronic structure of olivine Li(1-x)CoPO(4), 4.8 V positive electrode material for lithium ion batteries, were investigated using the X-ray absorption spectroscopy (XAS) technique. The threshold energy in the Co K-edge increased with electrochemical Li removal, indicating the oxidation of cobalt ions due to charge compensation. Moreover, P and O K-edge XAS showed a slight shift in threshold energy with Li removal. Although it is generally believed that the electrons of PO(4) polyanion do not contribute to the oxidation process, present experimental results indicate changes in the electronic structure around PO(4) units. Such results would be interpreted by the idea of the hybridization effect between the Co 3d and O 2p orbitals and of the polarization effect introduced by Li ions. 相似文献
A series of cobalt(II) complexes having terpyridine derivatives such as 2,2′:6′,2″-terpyridine (1), 4,4′,4″-tBu3-2,2′:6′,2″-terpyridine (2), 5,5″-Me2-2,2′:6′,2″-terpyridine (3), 6,6″-Me2-2,2′:6′,2″-terpyridine (4) and 6,6″-(3,5-Me2C6H3)2-2,2′:6′,2″-terpyridine (5) was synthesized. The structures of 1, 3, and 4 were confirmed by X-ray crystallography. The coordination sphere around the cobalt center in 1 can be described as pseudo square pyramidal. On the other hand, complex 4 has pseudo trigonal bipyramidal structure. Upon activation with d-MAO (dried-methylaluminoxane), these complexes showed high activities for the polymerization of norbornene (NBE). In particular, polymerization of NBE with 4/d-MAO system at room temperature resulted in quantitative yield within several hours to give the polymers with relatively narrow molecular weight distributions and controlled molecular weight. The polymerizations of NBE with these cobalt catalyst systems proceeded in vinyl addition polymerization, which was confirmed by 1H NMR spectra of the resulting polymers. 相似文献
The reaction of enynals 1, including o-alkynylbenzaldehydes, and carbonyl compounds 2 in the presence of a catalytic amount of AuBr3 in 1,4-dioxane at 100 degrees C gave the functionalized aromatic compounds 3 in high yields. The AuBr3-catalyzed formal [4 + 2] benzannulation proceeds most probably through the coordination of the triple bond of 1 to AuBr3, the formation of a pyrylium auric ate complex via the nucleophilic addition of the carbonyl oxygen atom, the reverse electron demand-type Diels-Alder addition of the enols, derived from 2, to the auric ate complex, and subsequent dehydration and bond rearrangement. Similarly, the AuBr3-catalyzed reactions of 1 with acetal compounds afforded the corresponding aromatic compounds in good yields. 相似文献
The recent development of new migration methods of micro-particles in liquids using various external fields is reviewed. The combination of a laser scattering force and a photothermal effect produced photothermal-conversion laser-photophoresis. A dielectric field generated in a planer or a capillary quadrupole electrode realized dielectrophoresis. Using a micrometer-scaled magnetic field gradient, the "Magnetophoretic velocimetry" of micro-particles was invented. Furthermore, the Lorentz force generated by combining an electric field and a magnetic field was utilized for electromagnetophoresis. These new methods were overlooked and the advantages in analytical use were discussed. 相似文献