Bulletin of the Chemical Society of Japan

Vol. 71, No. 03 (March, 1998)

RETRUN to the front page

Copyright (C) 1998 by The Chemical Society of Japan


CONTENTS


=============================
Accounts
=============================

Electrochemical Lithium Intercalation within Carbonaceous Materials: Intercalation Processes, Surface Film Formation, and Lithium Diffusion

GO TO the graphical abstract

Zempachi Ogumi* and Minoru Inaba

pages 521-534



=============================
Headline Articles
=============================

Preparation and Characterization of Inclusion Complexes of Poly(alkyl vinyl ether) with Cyclodextrins

GO TO the graphical abstract

Akira Harada,* Miyuko Okada, and Mikiharu Kamachi*

pages 535-542



=============================
Articles
General and Physical
=============================

Combined Effects of the Polarity of Terminal Groups and the Direction of Ester Linkages on Crystalline and Mesophase Structures of Biphenyl Esters with a Cyano or a Methoxy Group

GO TO the graphical abstract

Mutsuko Oki and Kayako Hori*

pages 543-548


Some Theoretical Considerations Concerning Ion Hydration in the Case of Ion Transfer between Water and 1,2-Dichloroethane

GO TO the graphical abstract

C. Snchez, E. Leiva,* S. A. Dassie, and A. M. Baruzzi

pages 549-554


Membrane Phenomena in Nonisothermal Systems: Part 3. Thermal Membrane Potential across Various Hydrophobic Anion-Exchange Membranes with 10 and 14% Divinylbenzene

GO TO the graphical abstract

Masud Shamsul Huda, Ryotaro Kiyono, Masayasu Tasaka,* Takanori Yamaguchi, and Toshikatsu Sata

pages 555-562


Catalytic Reforming of Methane with Carbon Dioxide on LaBO3 (B=Co , Ni, Fe, Cr) Catalysts

GO TO the graphical abstract

Yunying Wu, Osamu Kawaguchi, and Tsuneo Matsuda*

pages 563-572


Hubbard and Heisenberg Models for Four-Site Four-Electron Systems. Group-Theoretical Interrelationships and Applications to Multinuclear Transition-Metal Clusters

GO TO the graphical abstract

Yasunori Yoshioka,* Shigehiro Kubo, Shinji Kiribayashi, Yu Takano, and Kizashi Yamaguchi*

pages 573-588


Concentrated Salt Effects on the Solvolysis Reaction Rates in Methanol-Water Solution

GO TO the graphical abstract

Ludovick Christian Manege, Tadaharu Ueda, and Masashi Hojo*

pages 589-596



=============================
Articles
Analitical and Inorganic
=============================

Sequential Titrimetric and Spectrophotometric Determinations of Trace Amounts of Tin(II) and Tin(IV) by Amplification Reactions

GO TO the graphical abstract

Mohammed S. El-Shahawi,* and Ali Z. Abu Zuhri

pages 597-601


Catalytic Effect of N , N -Dimethyl-4-(2-pyridylazo)aniline on the Extraction Rate of Ni(II) with 1-(2-Pyridylazo)-2-naphthol: Ligand-Substitution Mechanism at the Liquid-Liquid Interface

GO TO the graphical abstract

Yuki Onoe, Satoshi Tsukahara, and Hitoshi Watarai*

pages 603-608


Kinetics and Mechanisms of Hydrogen Peroxide Disproportionation Catalyzed by Mononuclear Schiff Base Manganese(III) Complexes: Effects of Chelate and Hydroxide Ion on Hydrogen Peroxide Disproportionation in N , N -Dimethylformamide

GO TO the graphical abstract

Minori Uehara, Mika Urade, and Yuriko Abe*

pages 609-617


Mechanistic Studies on Cyclopalladation of the Solvated Palladium(II) Complexes with N -Benzyl Triamine Ligands in Various Solvents. Crystal Structures of [Pd(Sol)(Bn2 Medptn)](BF4 )2 (Sol = Acetonitrile and N , N -Dimethylformamide; Bn2 Medptn = N , N' -Dibenzyl-4-methyl-4-azaheptane-1,7-diamine) and [Pd(H-1 Bn2 Medptn- C , N , N' , N'' )]CF3 SO3

GO TO the graphical abstract

Takeyoshi Yagyu, Sen-ichi Aizawa, and Shigenobu Funahashi*

pages 619-629


Syntheses and Structures of Trinuclear Molybdenum Cluster Complexes [Mo3 S4 Cl4 (C5 H5 N)5 ] and [Mo3 S4 Cl3 (C5 H5 N)6 ]I

GO TO the graphical abstract

Jun Mizutani, Setsuko Yajima, Hideo Imoto, and Taro Saito*

pages 631-636


Preparations, Structures, and Properties of Cu(II) Complexes with Tripodal Tetradentate Ligand, Tris(6-pivaloylamino-2-pyridylmethyl)amine (Htppa), and Reaction of Its Cu(I) Complex with Dioxygen

GO TO the graphical abstract

Manabu Harata, Koichiro Jitsukawa,* Hideki Masuda,* and Hisahiko Einaga

pages 637-645


Determination of Ultratrace Gallium in River Water by Electrothermal Atomic Absorption Spectrometry after Preconcentration with Solvent Extraction and Back Extraction

GO TO the graphical abstract

Hiroshi Kawaguchi,* Tokuo Shimizu, Takashi Shirakashi, and Yoshio Shijo

pages 647-650


Solvatochromic Linear Solvation Energy Relationships for Solubility of O2 in Various Solvents

GO TO the graphical abstract

Yong Che, Koichi Tokuda, and Takeo Ohsaka*

pages 651-656


Calix[4]arene-Modified Oligosiloxane as a Quasi-Immobilized Neutral Carrier for Silicone-Rubber-Membrane Sodium Ion-Selective Electrodes

GO TO the graphical abstract

Keiichi Kimura,* Yutaka Tsujimura, Masaaki Yokoyama, and Takumi Maeda

pages 657-660


Preparation, Stereochemistry, and Reactivity of Linear-Type S-Bridged MCrIII M (M=RhIII , IrIII ) Trinuclear Complexes with 2-Aminoethanethiolate (aet). Crystal Structures of -[Cr{M(aet)3 }2 ]3+

GO TO the graphical abstract

Yoshitaro Miyashita, Narumi Sakagami, Yasunori Yamada, Takumi Konno, Jinsai Hidaka, and Ken-ichi Okamoto*

pages 661-670


Dioxygen Oxidation of Coordinated Nitrosyl to Nitro on Dmf-Bridged Dinuclear CoPb Complex

GO TO the graphical abstract

Hideki Furutachi and Hisashi kawa*

pages 671-677



=============================
Articles
Orgainc and Biological
=============================

Interglycosidic Acetals IV. Preparation and Regioselective Cleavage of Phenyl 2,2' : 4,6 : 4' ,6' -Tri- O -benzylidene-1-thio- -laminaribiosides

GO TO the graphical abstract

Nobuo Sakairi,* Yasunori Okazaki, Jun-ichi Furukawa, Hiroyoshi Kuzuhara, Norio Nishi, and Seiichi Tokura

pages 679-683


Solvolysis of 1-[ trans -2-( m - or p -Substituted Phenyl)cyclopropyl]-1-methylethyl p -Nitrobenzoates

GO TO the graphical abstract

Yoshiaki Kusuyama

pages 685-691


Synthesis and Properties of 9-(Tropylidenehydrazono)fluorene and Related Compounds

GO TO the graphical abstract

Masahiro Minabe,* Toshiya Nozawa, Tomoko Kurose, Takao Kimura, and Motohiro Tsubota

pages 693-697


Design and Synthesis of Peptides Passing through the Blood-Brain Barrier

GO TO the graphical abstract

Tateaki Wakamiya,* Makoto Kamata, Shoichi Kusumoto, Hiroyuki Kobayashi, Yoshimichi Sai, Ikumi Tamai, and Akira Tsuji

pages 699-709


Photodimerizations of 1,5- and 1,7-Azulenequinones: Solvent, Substituent, and Concentration Effects on the Product Distribution

GO TO the graphical abstract

Hiroko Kawakami, Yong Zhe Yan, Nobuo Kato, Akira Mori,*, Hitoshi Takeshita, and the late Tetsuo Nozoe

pages 711-716


The Reaction of Phthalic Anhydride with Diethylenetriamine and Triethylenetetramine. A Literature Correction

GO TO the graphical abstract

Anatoli Onopchenko,* James J. Harrison, and Carrie Y. Chan

pages 717-721


Direct Carbonylation of Benzyl Alcohol and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies

GO TO the graphical abstract

Yong-Shou Lin and Akio Yamamoto*

pages 723-734


Optical Resolution by Preferential Crystallization of ( RS )-Bromosuccinic Acid

GO TO the graphical abstract

Tadashi Shiraiwa,* Masanori Ohkubo, Hideya Miyazaki, Motoki Kubo, Hiroki Nishigawa, Toshihiro Tsujimoto, and Hidemoto Kurokawa

pages 735-739


Lithiosilanes with Si-Si Bonds: Synthesis and 6 Li, 7 Li, and 29 Si NMR Studies

GO TO the graphical abstract

Masato Nanjo, Akira Sekiguchi,* and Hideki Sakurai,*,

pages 741-747


Dimensiosolvatic Effects. III. Quantification of Dimensiosolvatic Effects by Solvolyses of 2-Bromoadamantane in Water-Alcohol Mixtures

GO TO the graphical abstract

Michinori ki,* Hiroshi Ikeda, and Shinji Toyota

pages 749-754



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 71, No. 03 (March, 1998)

RETRUN to the front page

Copyright (C) 1998 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


=============================
Accounts
=============================


Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 521-534 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Electrochemical Lithium Intercalation within Carbonaceous Materials: Intercalation Processes, Surface Film Formation, and Lithium Diffusion

Zempachi Ogumi* and Minoru Inaba


Illustration

Electrochemical lithium intercalation within carbonaceous materials has attracted much attention for use to produce anodes in rechargeable lithium batteries. This review article covers recent topics of the lithium intercalation, focusing on three fundamental aspects: intercalation processes, surface film formation, and lithium diffusion within carbons.

Return to the table of contents [next] [category] [top]

=============================
Headline Articles
=============================


Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 535-542 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Preparation and Characterization of Inclusion Complexes of Poly(alkyl vinyl ether) with Cyclodextrins

Akira Harada,* Miyuko Okada, and Mikiharu Kamachi*


Illustration

-Cyclodextrin has been found to form inclusion complexes with poly(alkyl vinyl ether)s of various molecular weights to give stoichiometric compounds in crystalline states. The complexes were characterized by IR, 1 H NMR, 13 C NMR, and X-ray, thermal and elemental analyses. The structures of the complexes are discussed.

Return to the table of contents [next] [category] [top]

=============================
Articles
General and Physical
=============================


Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 543-548 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Combined Effects of the Polarity of Terminal Groups and the Direction of Ester Linkages on Crystalline and Mesophase Structures of Biphenyl Esters with a Cyano or a Methoxy Group

Mutsuko Oki and Kayako Hori*


Illustration

Crystal structures have been determined for the indicated compounds. A combination of opposite polarity of the terminal groups and opposite direction of the central ester linkages results in almost the same crystalline and monolayered smectic A structures.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 549-554 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Some Theoretical Considerations Concerning Ion Hydration in the Case of Ion Transfer between Water and 1,2-Dichloroethane

C. Snchez, E. Leiva,* S. A. Dassie, and A. M. Baruzzi


Illustration

Some aspects of direct ion transfer across water/1,2-dichloroethane were analyzed using a very simple model based on thermodynamic considerations. It was concluded that ion solvation by water molecules may occur in some particular cases in the organic phase, delivering an important contribution to the Gibbs free energy of ion transfer between the aqueous and organic phases.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 555-562 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Membrane Phenomena in Nonisothermal Systems: Part 3. Thermal Membrane Potential across Various Hydrophobic Anion-Exchange Membranes with 10 and 14% Divinylbenzene

Masud Shamsul Huda, Ryotaro Kiyono, Masayasu Tasaka,* Takanori Yamaguchi, and Toshikatsu Sata


Illustration

The thermal membrane potential ( ) across anion-exchange membranes having benzyltrialkylammonium groups was measured. The order of || was Cl->Br->I- , which corresponds to that of the B -coefficient for viscosity. For large oxoanions || was NO3->IO3->SO42- and the water term in played an important role.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 563-572 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Catalytic Reforming of Methane with Carbon Dioxide on LaBO3 (B=Co , Ni, Fe, Cr) Catalysts

Yunying Wu, Osamu Kawaguchi, and Tsuneo Matsuda*


Illustration

The reforming reactions of CH4 with CO2 on perovskite structural oxides, LaBO3 (B=Co , Ni, Fe, Cr), were examined. The reaction activity at 1073 K followed the order LaCoO3>LaNiO3>LaFeO3>LaCrO3 . During the reforming reaction both LaCoO3 and LaNiO3 catalysts were decomposed by reduction to Co or Ni metal and La2 O3 .

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 573-588 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Hubbard and Heisenberg Models for Four-Site Four-Electron Systems. Group-Theoretical Interrelationships and Applications to Multinuclear Transition-Metal Clusters

Yasunori Yoshioka,* Shigehiro Kubo, Shinji Kiribayashi, Yu Takano, and Kizashi Yamaguchi*


Illustration

Hubbard models for four-site four-electron {4,4} systems are analytically solved to elucidate group-theoretical interrelationships between effective Hamiltonians for radical characters, metal clusters, Cu4 O4 , and so on. In order to show interrelationships, the electronic states with D4h , Td , and D3h symmetries are constructed by use of the magnetically ordered general spin orbitals which have been determined by the GHF calculations. The spin-optimized SCF solutions examined here are equivalent to the full CI wavefunctions satisfying both spatial and spin symmetries.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 589-596 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Concentrated Salt Effects on the Solvolysis Reaction Rates in Methanol-Water Solution

Ludovick Christian Manege, Tadaharu Ueda, and Masashi Hojo*


Illustration

For typical SN 1 substrates, such as 1-adamantyl bromide and t -butyl chloride, the pseudo-first-order reaction rates (k /s-1 ) increased exponentially with increasing concentration of LiClO4 , NaClO4 , Mg(ClO4 )2 , and Ba(ClO4 )2 . The larger positive effects of metal perchlorates were explained by the change in the solvent structure and the formation of ``stable'' carbocations.

Return to the table of contents [next] [category] [top]

=============================
Articles
Analitical and Inorganic
=============================


Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 597-601 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Sequential Titrimetric and Spectrophotometric Determinations of Trace Amounts of Tin(II) and Tin(IV) by Amplification Reactions

Mohammed S. El-Shahawi,* and Ali Z. Abu Zuhri

In an aqueous acidic solution (pH 2.2-3.5) periodate ions reacted with tin(II), and the released iodate reacted with I- as follows:

Alternatively, the released iodine was extracted into chloroform and reduced with sodium sulfite and the produced I- was reacted with IO4 - as follow:

These reactions were used for titrimetric and spectrophotometric determinations of tin(II).

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 603-608 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Catalytic Effect of N , N -Dimethyl-4-(2-pyridylazo)aniline on the Extraction Rate of Ni(II) with 1-(2-Pyridylazo)-2-naphthol: Ligand-Substitution Mechanism at the Liquid-Liquid Interface

Yuki Onoe, Satoshi Tsukahara, and Hitoshi Watarai*


Illustration

N ,N -Dimethyl-4-(2-pyridylazo)aniline (PADA) significantly accelerated the extraction rate of Ni(II) with 1-(2-pyridylazo)-2-naphthol (Hpan). The ring closure process of Hpan in the coordination to Ni(pada)2+ adsorbed at the interface was found to be the rate-determining step by kinetic studies and molecular mechanics calculation.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 609-617 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Kinetics and Mechanisms of Hydrogen Peroxide Disproportionation Catalyzed by Mononuclear Schiff Base Manganese(III) Complexes: Effects of Chelate and Hydroxide Ion on Hydrogen Peroxide Disproportionation in N , N -Dimethylformamide

Minori Uehara, Mika Urade, and Yuriko Abe*


Illustration

The overall catalase-like activity of H2 O2 disproportionation coupled with the Mn(III)-Mn(IV) cycle is in the following order: saltnOH>salensaltnOCOPh>saltn . The large activity for the saltnOH complex with the 1,3-diamine ligand suggests stabilization of the transition state for the formation of hydrogen-bondings among the Mn(IV) intermediates and H2 O2 . For the salen complex in the presence of the OH- ion, the appearance of the reaction path involving not only the Mn(III)-Mn(IV) cycle, but also the Mn(II)-Mn(III) cycle, is due to the formation of the [Mn(salen)OH] complex.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 619-629 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Mechanistic Studies on Cyclopalladation of the Solvated Palladium(II) Complexes with N -Benzyl Triamine Ligands in Various Solvents. Crystal Structures of [Pd(Sol)(Bn2 Medptn)](BF4 )2 (Sol = Acetonitrile and N , N -Dimethylformamide; Bn2 Medptn = N , N' -Dibenzyl-4-methyl-4-azaheptane-1,7-diamine) and [Pd(H-1 Bn2 Medptn- C , N , N' , N'' )]CF3 SO3

Takeyoshi Yagyu, Sen-ichi Aizawa, and Shigenobu Funahashi*


Illustration

The kinetics of cyclopalladation for the solvated palladium(II) complexes with N -benzyl triamine ligands are reported. The reaction mechanism is discussed on the basis of the solvent, kinetic isotope, and steric effects.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 631-636 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Syntheses and Structures of Trinuclear Molybdenum Cluster Complexes [Mo3 S4 Cl4 (C5 H5 N)5 ] and [Mo3 S4 Cl3 (C5 H5 N)6 ]I

Jun Mizutani, Setsuko Yajima, Hideo Imoto, and Taro Saito*


Illustration

A trinuclear molybdenum cluster complex [Mo3 S4 Cl4 (C5 H5 N)5 ] was synthesized by the excision reaction of Mo3 S7 Cl4 with PPh3 and pyridine. By the reaction of [Mo3 S4 Cl4 (C5 H5 N)5 ] with I2 in pyridine, [Mo3 S4 Cl3 (C5 H5 N)6 ]I was synthesized.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 637-645 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Preparations, Structures, and Properties of Cu(II) Complexes with Tripodal Tetradentate Ligand, Tris(6-pivaloylamino-2-pyridylmethyl)amine (Htppa), and Reaction of Its Cu(I) Complex with Dioxygen

Manabu Harata, Koichiro Jitsukawa,* Hideki Masuda,* and Hisahiko Einaga


Illustration

Mononuclear copper complex with a tripodal tetradentate ligand, Htppa, has been prepared as a model of copper enzymes, whose structures and properties have been examined. Reaction of Cu(I)-Htppa with dioxygen gave CuII -O2 - species, and alternate bubblings of O2 /CO to the solution exhibited a reversible binding of O2 .

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 647-650 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Determination of Ultratrace Gallium in River Water by Electrothermal Atomic Absorption Spectrometry after Preconcentration with Solvent Extraction and Back Extraction

Hiroshi Kawaguchi,* Tokuo Shimizu, Takashi Shirakashi, and Yoshio Shijo


Illustration

Gallium is extracted into carbon tetrachloride as an ion pair of Ga-5-sulfo-8-quinolinol (H2 QS) chelate anion with tetradecyldimethylbenzylammonium chloride (Zephiramine), and subsequently back-extracted into 0.3 cm3 of nitric acid solution. The detection limit for Ga is 0.29 ng dm-3 , based on 1500-fold preconcentration.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 651-656 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Solvatochromic Linear Solvation Energy Relationships for Solubility of O2 in Various Solvents

Yong Che, Koichi Tokuda, and Takeo Ohsaka*


Illustration

Solvatochromic linear solvation energy relationships for solution of O2 in 27 solvents have been examined, and multiple linear regression equations for mole fraction solubility of O2 are developed based on solvent parameters H2 , * , , and .

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 657-660 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Calix[4]arene-Modified Oligosiloxane as a Quasi-Immobilized Neutral Carrier for Silicone-Rubber-Membrane Sodium Ion-Selective Electrodes

Keiichi Kimura,* Yutaka Tsujimura, Masaaki Yokoyama, and Takumi Maeda


Illustration

An oligomeric calix[4]arene ionophore having medium molecular weight is promissing as a quasi-immobilized neutral carrier for durable sodium-ion-selective silicone-rubber-membrane electrodes.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 661-670 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Preparation, Stereochemistry, and Reactivity of Linear-Type S-Bridged MCrIII M (M=RhIII , IrIII ) Trinuclear Complexes with 2-Aminoethanethiolate (aet). Crystal Structures of -[Cr{M(aet)3 }2 ]3+

Yoshitaro Miyashita, Narumi Sakagami, Yasunori Yamada, Takumi Konno, Jinsai Hidaka, and Ken-ichi Okamoto*


Illustration

S-Bridged trinuclear complexes, [CrIII {M(aet)3 }2 ]3+ , (M=RhIII ( 1 ), IrIII ( 2 ); aet=NH2CH2CH2S- ) were newly prepared, and their isomers were characterized by the electronic absorption and CD spectra, the molar conductivity, and the magnetic susceptibility. A cyclic voltammogram in water showed a reversible redox couple (M(IV)/M(III)) and an irreversible reduction wave (Cr(III)/Cr(II)). The stabilities of the S-bridged MCrIII M complexes are also discussed.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 671-677 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Dioxygen Oxidation of Coordinated Nitrosyl to Nitro on Dmf-Bridged Dinuclear CoPb Complex

Hideki Furutachi and Hisashi kawa*


Illustration

A nitrosyl CoPb complex is oxidized with dioxygen to a nitro complex; both complexes are characterized by X-ray crystallography and NMR spectroscopies.

Return to the table of contents [next] [category] [top]

=============================
Articles
Orgainc and Biological
=============================


Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 679-683 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Interglycosidic Acetals IV. Preparation and Regioselective Cleavage of Phenyl 2,2' : 4,6 : 4' ,6' -Tri- O -benzylidene-1-thio- -laminaribiosides

Nobuo Sakairi,* Yasunori Okazaki, Jun-ichi Furukawa, Hiroyoshi Kuzuhara, Norio Nishi, and Seiichi Tokura


Illustration

A novel tri-O -benzylidene derivative of 1-thio- -laminaribioside having an unusual eight-membered ring was prepared by acid-catalyzed trimolar benzylidenation of phenyl 1-thio- -laminaribioside. A regioselective ring opening of the benzylidene acetal afforded partially protected disaccharides.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 685-691 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Solvolysis of 1-[ trans -2-( m - or p -Substituted Phenyl)cyclopropyl]-1-methylethyl p -Nitrobenzoates

Yoshiaki Kusuyama


Illustration

The solvolyses of 1-[trans -2-(m - or p -substituted phenyl)-cyclopropyl]-1-methylethyl p -nitrobenzoates in 80% aqueous acetone were examined, giving rate constants and product distributions. The solvolyses proceed via two independent reaction pathways: One intermediate is the corresponding cyclopropylmethyl cation and the other is the homoallylic cation.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 693-697 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Synthesis and Properties of 9-(Tropylidenehydrazono)fluorene and Related Compounds

Masahiro Minabe,* Toshiya Nozawa, Tomoko Kurose, Takao Kimura, and Motohiro Tsubota


Illustration

9-(Tropylidenehydrazono)fluorene ( 1 ) was obtained by the reaction of 9-fluorenone hydrazone ( 2 ) with tropylium salt ( 3 ), accompanied by 9-fluorenone azine, 9-(benzylidenehydrazono)fluorene, and 9,9-ditropylfluorene. The amination of 1 occurred at the 2-position of the tropylidene moiety. The reaction of 1 with tosyl isocyanate afforded the [8+2 ] adduct.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 699-709 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Design and Synthesis of Peptides Passing through the Blood-Brain Barrier

Tateaki Wakamiya,* Makoto Kamata, Shoichi Kusumoto, Hiroyuki Kobayashi, Yoshimichi Sai, Ikumi Tamai, and Akira Tsuji


Illustration

A basic peptide termed 001-C8 ( 1 ) was synthesized as a novel compound passing through the blood-brain barrier (BBB). Furthermore, a number of basic peptides as 001-C8 analogs were prepared for studying the relationship between structure and BBB permeability of peptides.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 711-716 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Photodimerizations of 1,5- and 1,7-Azulenequinones: Solvent, Substituent, and Concentration Effects on the Product Distribution

Hiroko Kawakami, Yong Zhe Yan, Nobuo Kato, Akira Mori,*, Hitoshi Takeshita, and the late Tetsuo Nozoe


Illustration

Irradiation of azulenequinones gave head-to-head dimers predominantly in polar solvents and head-to-tail dimers increased in less polar solvents. Methoxyazulenequinone gave four products, while others gave a single head-to-head dimer. The solvent polarity, substituent, and concentration reflected on the product distribution.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 717-721 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

The Reaction of Phthalic Anhydride with Diethylenetriamine and Triethylenetetramine. A Literature Correction

Anatoli Onopchenko,* James J. Harrison, and Carrie Y. Chan


Illustration

Contrary to a recent report, phthalic anhydride reacts with diethylenetriamine in HOAc to give the corresponding bis(phthalimide), some amide, and little of its hydrogen phthalate salt. Linear triethylenetetramine gives amide of the corresponding bis(phthalimide) instead, and no rearranged isomers reported.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 723-734 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Direct Carbonylation of Benzyl Alcohol and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies

Yong-Shou Lin and Akio Yamamoto*

Pd-catalyzed carbonylation of benzyl alcohol ( 1 ) and its analogs to phenylacetic acid ( 2 ) promoted by HI in aqueous systems has been achieved in excellent yields.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 735-739 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Optical Resolution by Preferential Crystallization of ( RS )-Bromosuccinic Acid

Tadashi Shiraiwa,* Masanori Ohkubo, Hideya Miyazaki, Motoki Kubo, Hiroki Nishigawa, Toshihiro Tsujimoto, and Hidemoto Kurokawa

(RS )-Bromosuccinic acid [(RS )-BSA] was found to exist as a conglomerate at room temperature and to form a racemic compound at the melting point. The optical resolution by preferential crystallization gave (R )- and (S )-BSA of 81-93% optical purities. (RS )-BSA was also optically resolved using (1S ,2S )-2-amino-1-phenyl-1,3-propanediol, as a resolving agent, to afford (R )- and (S )-BSA of 99 and 83% optical purities, respectively.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 741-747 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Lithiosilanes with Si-Si Bonds: Synthesis and 6 Li, 7 Li, and 29 Si NMR Studies

Masato Nanjo, Akira Sekiguchi,* and Hideki Sakurai,*,


Illustration

Unsolvated and aggregated lithiosilanes with Si-Si bonds have been synthesized via lithium-mercury exchange reactions in toluene. NMR spectroscopic studies reveal that the unsolvated lithiosilanes exist as the aggregated oligomers in a non-polar solvent, whereas those solvated by THF or Et2 O exist as monomers.

Return to the table of contents [next] [category] [top]

Copyright (C) 1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 71, 749-754 (1998) [Vol. 71, No. 3, March, 1998]

Return to the table of contents [next] [category] [top]

Dimensiosolvatic Effects. III. Quantification of Dimensiosolvatic Effects by Solvolyses of 2-Bromoadamantane in Water-Alcohol Mixtures

Michinori ki,* Hiroshi Ikeda, and Shinji Toyota


Illustration

The selectivity in solvolysis of 2-bromoadamantane was found to be practically constant at various temperatures for a given alcohol, if the alcohol-water ratio of 1.0 : 0.8 was taken. The reciprocals of the S values, D 's, were proposed to be measures of the dimensiosolvatic effects for the solvent intervention into contact ion pairs.

Return to the table of contents [next] [category] [top]