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Makoto Fujita*,,
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Articles
General and Physical
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*
-Type Triplet State
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g+
) with Some Simple Molecules at Room Temperature
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Kiyotaka Asakura,,
Khirui Tsai,
and
Yasuhiro Iwasawa*
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Naoto Kijima, and
Tokuko Watanabe
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Articles
Analitical and Inorganic
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Masahiro Mikuriya,*,
Hiroshi Azuma,
and
Kuninobu Kasuga
3
-Propargylpalladium Complexes
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Yuji Okada,
and
Hideo Kurosawa*,
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and
Hideo Akaiwa
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and
Kazuchika Ohta,*,
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Articles
Orgainc and Biological
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-amino Acids and Application to the Synthesis of 1-Azabicyclic Alkaloids
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Yasushi Imada, and
Shun-Ichi Murahashi*
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and
Masahito Ochiai
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and
Tadamitsu Sakurai*
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Articles
Applied and Materials
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Copyright (C) 1999 The Chemical Society of Japan
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Accounts
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Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2573-2590 (1999) [Vol. 72, No. 12, December, 1999]
Electrochemical reduction of H2 O2 on Pt electrodes shows various oscillations, depending on the electrode potential, the atomic-level flatness of the electrode surface, and the presence of adsorbed metal and halogen atoms. The general behavior, mechanisms, and features are surveyed.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2591-2602 (1999) [Vol. 72, No. 12, December, 1999]
This account describes recent development in carbon-carbon bond cleavage reactions and selective transformation of 5-membered zirconacycles including zirconacyclopentanes, zirconacyclopentenes and zirconacyclopentadienes.
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Headline Articles
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Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2603-2606 (1999) [Vol. 72, No. 12, December, 1999]
Makoto Fujita*,,
The formation of ...Pt(II)...Br-Pt(IV)... mixed-valence complexes was utilized for the assembly of Pt(II) containing macrocyclic complexes: e.g., the reaction of [(en)Pt(4,4' -bpy)]4 (NO3 )8 ( 1 , 4,4' -bpy = 4 ,4' -bipyridine) with [PtBr2 (en)2 ]Br2 gave a stair-like infinite network.
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Articles
General and Physical
=============================
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2607-2615 (1999) [Vol. 72, No. 12, December, 1999]
The choatic response of the minimal chemical oscillator stimulated by a sinusoidal perturbation was studied by computer simulation. There were two types of chaos. The properties of these two types are described in detail and compared with the behaviors of a one-dimensional dynamical system.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2617-2623 (1999) [Vol. 72, No. 12, December, 1999]
Under cathodic polarization, emission of ZnGa2 O4 electrode showed a broad peak at 485 nm in Na2 S2 O8 electrolyte, while under strong anodic polarization at +12.5 V (vs. Ag/AgCl), electrochemical luminescence was observed accompanied by avalanche breakdown of the depletion layer of the ZnGa2 O4 electrode based on a impact excitation mechanism.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2625-2632 (1999) [Vol. 72, No. 12, December, 1999]
*
-Type Triplet State
Time-resolved ESR spectra of ketyl and anion radicals in the photoreduction of aromaticketone/triethylamine systems were measured. Anion radicals with absorption spin polarization were produced in ethanol with KOH, while ketyl radicals with emissive polarization were formed in cyclohexane and benzene. Possible CIDEP mechanisms were discussed for both radicals.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2633-2641 (1999) [Vol. 72, No. 12, December, 1999]
g+
) with Some Simple Molecules at Room Temperature
A multiphoton dissociation of volatile metal carbonyls was applied for pulse production of neutral metal species in the gas-phase kinetic study and its feasibility was discussed in the reaction system of Mo2
with small molecules at room temperature.
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Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2643-2653 (1999) [Vol. 72, No. 12, December, 1999]
Kiyotaka Asakura,,
Khirui Tsai,
and
Yasuhiro Iwasawa*
A reversible structure transformation of SiO2 -supported Au6 Pt cluster by the adsorption-desorption of CO without any fragmentation of the Au6 Pt framework was observed by EXAFS as shown in the scheme below. The H2 adsorption at 298 K was weak and showed almost no contribution to the EXAFS.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2655-2664 (1999) [Vol. 72, No. 12, December, 1999]
Naoto Kijima, and
Tokuko Watanabe
89 Y MAS (Magic angle spinning) NMR was investigated in order to study the local environment of Y sites in a red phosphor, Eu doped-Y2 O2 S (Eu-Y2 O2 S), with varying Eu content. Despite the presence of paramagnetic Eu3+ ions, high resolution spectra were acquired and a number of local environments were detected.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2665-2671 (1999) [Vol. 72, No. 12, December, 1999]
A quantum control of the photodissocation of NaI 
NaI* Na + I
was theoretically studied by using a locally optimized control method. The control was based on the following pump-and-dump scheme. The optimal dump pulses were shown to be of a linear up-chirp type.
=============================
Articles
Analitical and Inorganic
=============================
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2673-2679 (1999) [Vol. 72, No. 12, December, 1999]
A flow-type chemiluminescence detection cell using an optical fiber was designed for capillary electrophoresis. Hydrogen peroxide was delivered through a three-way joint by a syringe pump and mixed with analytes at the capillary outlet. The present flow-type system provided a CL signal with high sensitivity, resolution, and reproducibility.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2681-2686 (1999) [Vol. 72, No. 12, December, 1999]
Masahiro Mikuriya,*,
Hiroshi Azuma,
and
Kuninobu Kasuga
Adduct polymers and dimers of rhodium(II) pivalate ([Rh2
(O2
CCMe3
)4
]) with pyrazine (pyz), 4,4'
-bipyridine (4,4'
-bpy), 1,4-diazabicyclo[2.2.2]octane (dabco), triethylamine (tea), and pyridine (py)) have been prepared. The tea adduct has a considerably long Rh-Rh bond (2.395(1) 
).
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2687-2692 (1999) [Vol. 72, No. 12, December, 1999]
3
-Propargylpalladium Complexes
Yuji Okada,
and
Hideo Kurosawa*,
The reactions of 1
-allenyl- and 1
-chloro(propargyl)palladium complexes with Ag+
afford cationic 3
-propargylpalladium complexes. The cationic 3
-propargylpalladium complex could be also observed as an equilibrium mixture with the 1
-allenyl(chloro)palladium one. The factors favoring 3
-coordination of the propargyl ligand are discussed.
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2693-2697 (1999) [Vol. 72, No. 12, December, 1999]
and
Hideo Akaiwa
The extracted species of rare earth elements (REEs) in bis(1,1,3,3-tetramethylbutyl)phosphinic acid (Hmbp)-HNO3 system was identified by the saturated extraction method, elemental analysis, IR, and 1 H NMR as being [M(mbp)3 (Hmbp)3 ] (M = REE ). The quantitative mutual separation of REEs was achieved on a Hmbp modified C18 column by high-performance extraction chromatography utilizing the characteristics of high selectivity and low acidity of Hmbp for REEs extraction, and pH gradient elution.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2699-2702 (1999) [Vol. 72, No. 12, December, 1999]
The pyrolysis of a polyoxovanadate solid, (NH4
)12
[V18
O42
(H2
O)].n
H2
O (n 
11
), at 300 °C in an Ar+NH3
atmosphere gave a mixed-valence vanadium oxide, (NH4
)x
V3
O7
(x 0.6
), with a tunnel-structure. (NH4
)x
V3
O7
comprises edge- and corner-sharing VIV/V
O5
square-pyramids with an approximate ratio of VIV : VV 0.49 : 0.51
, to form a columnar cavity which accommodates ammonium N atoms.
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2703-2711 (1999) [Vol. 72, No. 12, December, 1999]
The solvent extraction of gallium(III) with Htta in toluene was enhanced by an addition of TOPO. TOPO also enhances the rate of extraction. The association of Htta and TOPO in toluene is very marked; the effects on the degree of and rate of extraction appear smaller than when no association is assumed. Extraction with Htta (
), with Htta+TOPO
(
, 
, 
, 
).
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2713-2717 (1999) [Vol. 72, No. 12, December, 1999]
A time-resolved surface-enhanced Raman measurement system was developed by combining step-scan and a near-infrared FT-Raman spectrometer. A redox reaction of 9,10-phenanethrenequinone on a gold electrode could be monitored in situ dynamically within 1 ms time resolution.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2719-2728 (1999) [Vol. 72, No. 12, December, 1999]
and
Kazuchika Ohta,*,
Triple-decker sandwich complexes, which consist of two cerium ions and three strip-like diarylporphyrins substituted by long alkoxyl chains, have been synthesized. Their spectroscopic and electrochemical properties and mesomorphism are reported and compared with those of the corresponding double deckers and the parent monomers.
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Articles
Orgainc and Biological
=============================
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2729-2736 (1999) [Vol. 72, No. 12, December, 1999]
The amide bond of 1a -lanthanide complex was efficiently cleaved to give 2a and ester almost quantitatively at 30 °C.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2737-2754 (1999) [Vol. 72, No. 12, December, 1999]
-amino Acids and Application to the Synthesis of 1-Azabicyclic Alkaloids
Yasushi Imada, and
Shun-Ichi Murahashi*
Tungstate-catalyzed oxidation of N
-alkyl-
-amino acids with hydrogen peroxide under phase-transfer conditions gives regiochemically defined nitrones in satisfactory yields. Chiral cyclic nitrones, readily prepared from 4-(t
-butyldimethylsilyloxy)-
L
-proline and 3-(t
-butyldimethylsilyloxy)pyrrolidine, are successfully applied to the asymmetric synthesis of the Geissman-Waiss lactone, a monohydroxylated pyrrolizidine, and a monohydroxylated indolizidine.
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2755-2760 (1999) [Vol. 72, No. 12, December, 1999]
The title compounds show only a smectic phase over a wide range of temperatures. The propionyl group is effective for the thermal stability of the mesophase compared to the acetyl group as an acyl substituent of the title substances. The Schiff base derived from 1- or 3-fluoreneamine scarcely shows liquid crystallinity.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2761-2769 (1999) [Vol. 72, No. 12, December, 1999]
and
Masahito Ochiai
Solvolysis of both E
and Z
isomers of the iodonium (
1
) tetrafluoroborate was carried out in various solvents at 60 °C. Extensive rearrangements mainly due to 
-alkyl participation followed by hydride shift were observed.
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2771-2780 (1999) [Vol. 72, No. 12, December, 1999]
and
Tadamitsu Sakurai*
The quantum yields for the sensitized photolysis of 1 in cationic micelles showed that 2 and 3 are derived from the radical pair existing at the micellar surface, whereas the radical pair that is penetrated deeply into the micellar interior is responsible for the appearance of 4 and 5 .
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2781-2783 (1999) [Vol. 72, No. 12, December, 1999]
Two conformationally frozen isomers (cone and 1,2,3-alternate) of a water-soluble calix[6]arene were synthesized and found to show the critical micelle concentrations quite different from each other, which was explained in terms of their monomer structures with different arrangements of the charged groups.
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=============================
Articles
Applied and Materials
=============================
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2785-2790 (1999) [Vol. 72, No. 12, December, 1999]
Two peaks assigned to the COO- symmetric and asymmetric vibrations were observed for the difference spectra between the saponified starch acetate and the native starch. The peak areas linearly increased with increasing the degree of substitution (dS), suggesting that the dS values can be evaluated from the correlation.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2791-2794 (1999) [Vol. 72, No. 12, December, 1999]
A disk was prepared with the powders of the oxygen-absorbing, but electrically insulating, 5,10,15,20-tetrakis(
-o
-pivalamidophenyl)porphyrinatocobalt(II)-N
-tritylimidazole complex and of electrically conductive carbon. A 1.5 V-application induced a temperature elevation in the disk, which momentarily released the absorbed oxygen. The oxygen-releasing and -absorbing cycle could be repeated quickly.
Copyright (C)
1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2795-2802 (1999) [Vol. 72, No. 12, December, 1999]
A novel monolayer preparation method which was referred to as cooling multi-step creep method was described. The cooling multi-step creep method could provide the defect-diminished crystalline monolayer by control of both the thermal molecular motion in the monolayer and the structural relaxation induced by the area-creep.
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1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
72, 2803-2806 (1999) [Vol. 72, No. 12, December, 1999]
The pressure and temperature dependence of the catalysis and fluorescence of carboxypeptidase Y was studied in the range of 5-40 °C and 0.1-400 MPa. In the high-pressure, lower-temperature region, disactivation and a fluorescence decrease were observed and explained by the so-called pressure-assisted cold-denaturation of the protein.
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