Bulletin of the Chemical Society of Japan

Vol. 68, No. 02 (February, 1995)

RETRUN to the front page

Copyright (C) 1995 by The Chemical Society of Japan


CONTENTS


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

Transition Metal-Catalyzed Synthesis of Silicon Polymers

GO TO the graphical abstract

Hiroshi Yamashita and Masato Tanaka *

pages 403-419


Structure and Reactivity of C2 Species on Polymetallic Systems

GO TO the graphical abstract

Munetaka Akita* and Yoshihiko Moro-oka

pages 420-432


Palladium-Catalyzed Double and Single Carbonylation of Aryl Halides and Allylic Compounds

GO TO the graphical abstract

Akio Yamamoto

pages 433-446



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

Nonlinearity of the Enthalpic Response Function to a Temperature Jump and Its Interpretation Based on Fragility in Liquid Glasses

GO TO the graphical abstract

Hiroki Fujimori, Hiroaki Fujita, and Masaharu Oguni*

pages 447-455


Dinuclear Oxomolybdenum(V) and Oxotungsten(V) Complexes of the Hexadentate Ligands N , N , N' , N' -Tetrakis(2-pyridylmethyl)ethylenediamine and Its Propylenediamine Analog

GO TO the graphical abstract

Ryoichi Hazama, Keisuke Umakoshi, Akio Ichimura, Shinji Ikari, Yoichi Sasaki,* and Tasuku Ito

pages 456-468



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

Structure, Composition, and Vibrational Property of Iodine-Doped Polyvinyl Alcohol Studied by Temperature-Dependent I K-Edge Extended X-Ray-Absorption Fine Structure

GO TO the graphical abstract

Toshihiko Yokoyama, Kentaro Kaneyuki, Hitoshi Sato, Hiroshi Hamamatsu, and Toshiaki Ohta*

pages 469-475


Electrochemical Impedance Study and Characteristics of Polyaniline Film Electrodes

GO TO the graphical abstract

Teruhisa Komura,* Hironobu Sakabayashi, and Koshin Takahashi

pages 476-480


Electro-Optical and Hydrodynamic Properties of Synthetic Polyribonucleotides in Solutions as Studied by Electric Birefringence

GO TO the graphical abstract

Masato Tanigawa and Kiwamu Yamaoka*

pages 481-492


Thermoosmosis and Transported Entropy of Water across Hydrocarbonsulfonic Acid-Type Cation-Exchange Membranes

GO TO the graphical abstract

Takashi Suzuki, Keiko Iwano, Ryotaro Kiyono, and Masayasu Tasaka*

pages 493-501


Interactions of Cu2+ and VO2+ Ions with Phosphatidylcholine Vesicular Membranes as Studied by the 1 H NMR Paramagnetic Relaxation Method

GO TO the graphical abstract

Hisao Tanaka,* Harumi Saito, and Hiroshi Kawazura

pages 502-505


Pressure Effect on the Inter- and Intramolecular Vibrations of Pyrazine Crystal

GO TO the graphical abstract

Masayoshi Maehara, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada

pages 506-511


Raman Spectroscopic Study on the Temperature Dependence of the Uncoupled O-D Stretching Band from HDO Molecules in Concentrated Aqueous Zn(ClO4 )2 Solutions

GO TO the graphical abstract

Yasuo Kameda,* Ikuko Sugawara, Ken-ichi Kijima, Takeshi Usuki, and Osamu Uemura

pages 512-518


A Heuristic Molecular-Dynamics Approach for the Prediction of a Molecular Crystal Structure

GO TO the graphical abstract

Nobuo Tajima, Takayuki Tanaka, Tomoko Arikawa, Takashi Sakurai, Shoichi Teramae, and Tsuneo Hirano*,

pages 519-527


Simulation of the Valence X-Ray Photoelectron Spectra of 16 Polymers by the Semiempirical HAM/3 MO Method Using the Model Molecules

GO TO the graphical abstract

Kazunaka Endo,* Chiaki Inoue, Yasuo Kaneda, Masayuki Aida, Naoya Kobayashi, and Delano P. Chong*,

pages 528-538


Hydrate Cluster Formation of Diol Compounds in Aqueous Solution

GO TO the graphical abstract

Satoru Takahashi and Nobuyuki Nishi*

pages 539-546


Electrical and Optical Properties of -(BETS)2 I3 and -(BEDT-STF)2 I3

GO TO the graphical abstract

Makoto Inokuchi, Hiroyuki Tajima,* Akiko Kobayashi, Toshiaki Ohta, Haruo Kuroda, Reizo Kato, Toshio Naito, and Hayao Kobayashi

pages 547-553



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

Binuclear Dioxomolybdenum(VI) Complexes of Flexibly-Bridged Hexadentate Tetraanionic Schiff's Bases Derived from Methylene- or Dithio-bis(salicylaldehyde) and S -Methyldithiocarbazate or S -Benzyldithiocarbazate

GO TO the graphical abstract

Mannar R. Maurya,* Deena C. Antony, Sarada Gopinathan, and Changaramponnath Gopinathan*,

pages 554-558


Silica Gel-Bonded Cationic Polyelectrolyte with Ferron as Counterion. Application to Preconcentration or Elimination of Trace Metals

GO TO the graphical abstract

Bhim Bali Prasad* and Sonu Sundd

pages 559-565


Observation of Nuclear Excitation by Electron Transition (NEET) in 197 Au with a Nanosecond Stroboscopic Electron Spectrometer

GO TO the graphical abstract

Atsushi Shinohara,*, Tadashi Saito, Kiyoteru Otozai, Hiromu Fujioka,, and Katsumi Ura,

pages 566-573


Syntheses and Structural Characterization of Dinuclear and Trinuclear Iron(II) Complexes of Tridentate Thiolic Ligands with an NNS Donor Set

GO TO the graphical abstract

Masahiro Mikuriya,* Takanori Kotera, Fumiya Adachi, Makoto Handa, Masayuki Koikawa,, and Hisashi kawa

pages 574-580


Molecular Structure of Nitro- and Nitrito-Copper Complexes as Reaction Intermediates in Electrochemical Reduction of Nitrite to Dinitrogen Oxide

GO TO the graphical abstract

Nobutoshi Komeda, Hirotaka Nagao, Yoshinori Kushi, Gin-ya Adachi, Masatatsu Suzuki, Akira Uehara, and Koji Tanaka*,

pages 581-589


Synergic Extraction Equilibrium of Mn(II) with 4,4,4-Trifluoro-1-(2-thienyl)-1,3-butanedione and Neutral Multidentate Ligands, Such as Terpyridine and Tetraphenyldiphosphane Dioxide

GO TO the graphical abstract

Saeko Satake, Satoshi Tsukahara,* and Nobuo Suzuki

pages 590-593


Analysis of d-d Transitions in [Cr(CN)(NH3 )5 ]2+ as Inferred from Polarized Optical Spectra and Angular Overlap Model Calculations

GO TO the graphical abstract

Akio Urushiyama,* Mutsuyoshi Itoh, and Thomas Schnherr

pages 594-603


Extraction Behavior of Di- -oxo-bis[oxomolybdenum(V)] with 2-Methyl-5-octyloxymethyl-8-quinolinol

GO TO the graphical abstract

Yuqi Feng, Hisanori Imura,* and Kousaburo Ohashi

pages 604-609


Synthesis and Properties of Linear-Type S-Bridged RhIII NiII RhIII Trinuclear Complexes with 2-Aminoethanethiolate (aet) or L -Cysteinate ( L -cys). Crystal Structure of [Ni{Rh(aet)3 }2 ](NO3 )2

GO TO the graphical abstract

Takumi Konno* and Ken-ichi Okamoto

pages 610-615



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

Synthesis and Photochromic Properties of Fulgides with a t -Butyl Substituent on the Furyl- or Thienylmethylidene Moiety

GO TO the graphical abstract

Jitsuo Kiji,* Tamon Okano, Hitoshi Kitamura, Yasushi Yokoyama,*, Shuji Kubota, and Yukio Kurita

pages 616-619


Antioxidant Activities of Aminophenols against Oxidation of Methyl Linoleate in Solution

GO TO the graphical abstract

Misato Iwatsuki, Erika Komuro, and Etsuo Niki*

pages 620-624


Triethylborane-Induced Radical Cyclization of 1-Allyloxy-2-halosilacyclopentane. Stereoselective Synthesis of 1,3,6-Triols Starting from Silacyclobutane

GO TO the graphical abstract

Kozo Matsumoto, Katsukiyo Miura, Koichiro Oshima,* and Kiitiro Utimoto*

pages 625-634


Synthesis and Molecular Structure of [4][34 ](1,2,3,4,5)Ferrocenophane

GO TO the graphical abstract

Masao Hisatome,* Jun Watanabe, Koji Yamakawa, Kozo Kozawa, and Tokiko Uchida

pages 635-644


Stereoselective Allylation of 2-Formyl Amides or 3-Oxo Amides

GO TO the graphical abstract

Masahiko Taniguchi, Koichiro Oshima,* and Kiitiro Utimoto*

pages 645-653


Synthesis and Properties of Cationic Organopalladium Complexes. Remarkable Rate Enhancement in Olefin Insertion into the Palladium-Aryl Bond by the Generation of a Cationic Palladium Complex from trans -[PdBr(Ph)(PMe3 )2 ]

GO TO the graphical abstract

Futoshi Kawataka, Isao Shimizu, and Akio Yamamoto*

pages 654-660


Synthesis, Properties, and Structures of 1,2 : 5,6-Bis(ethylenedithio)pyracylene and Its Radical Cation Salts

GO TO the graphical abstract

Hiroyuki Tani

pages 661-669


Short Synthesis of (3 S ,4 R )- and (3 R ,4 R )-3-Hydroxy-4-hydroxymethyl-4-butanolides, Two Lactones from Levoglucosenone

GO TO the graphical abstract

Katsuya Matsumoto,* Takashi Ebata, Koshi Koseki, Koji Okano, Hiroshi Kawakami, and Hajime Matsushita

pages 670-672


Solvent Effects on the Solvolysis of p -Nitrobenzyl and 3,5-Bis(trifluoromethyl)benzyl p -Toluenesulfonates

GO TO the graphical abstract

Mizue Fujio,* Toshihiro Susuki, Mutsuo Goto, Yutaka Tsuji, Ken-ichi Yatsugi, Sung Hong Kim, Gamal Abdel-Wahab Ahmed, and Yuho Tsuno

pages 673-682



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 68, No. 02 (February, 1995)

RETRUN to the front page

Copyright (C) 1995 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 403-419 (1995) [Vol. 68, No. 2, February, 1995]

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

Transition Metal-Catalyzed Synthesis of Silicon Polymers

Hiroshi Yamashita and Masato Tanaka *


Illustration

New efficient catalytic transformations with Si-H and Si-Si bonds promoted by early and late transition metal (Nd, Ru, Pt, Pd, etc.) complexes enable the synthesis and modification of various silicon polymers (polysilanes, polycarbosilanes, etc.). Possible key elemental processes depicted in the scheme are believed to take place in the catalyses.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 420-432 (1995) [Vol. 68, No. 2, February, 1995]

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

Structure and Reactivity of C2 Species on Polymetallic Systems

Munetaka Akita* and Yoshihiko Moro-oka


Illustration

Polymetallic C2 (C2 and C2 H) complexes are prepared by structure expansion of parent metal acetylide complexes, Fp* -CC-H and Fp* -CC-Fp* [Fp* =(5 -C5 Me5 )Fe(CO)2 ]. Their structure and reactivity have been investigated as models for surface-bound C2 species formed during catalytic CO hydrogenation.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 433-446 (1995) [Vol. 68, No. 2, February, 1995]

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

Palladium-Catalyzed Double and Single Carbonylation of Aryl Halides and Allylic Compounds

Akio Yamamoto


Illustration

After a brief summary on the double carbonylation of aryl halides, newly discovered single carbonylation of allylic formates and allylic chlorides to , -unsaturated carboxylic acids and the double carbonylation of allylic chlorides into , -unsaturated -keto amides are described along with a mechanistic discussion.

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

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 447-455 (1995) [Vol. 68, No. 2, February, 1995]

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

Nonlinearity of the Enthalpic Response Function to a Temperature Jump and Its Interpretation Based on Fragility in Liquid Glasses

Hiroki Fujimori, Hiroaki Fujita, and Masaharu Oguni*


Illustration

The irreversible enthalpy-relaxation processes of a liquid were tracked by the temperature jump method, and simulated based on a double-well potential model. The processes were found to show remarkable nonexponentialities and a nonlinearity to the temperature jump. The nonlinearity ( ) was interpreted to originate primarily from the fragility (m ), namely the non-Arrhenius property of the relaxation times.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 456-468 (1995) [Vol. 68, No. 2, February, 1995]

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

Dinuclear Oxomolybdenum(V) and Oxotungsten(V) Complexes of the Hexadentate Ligands N , N , N' , N' -Tetrakis(2-pyridylmethyl)ethylenediamine and Its Propylenediamine Analog

Ryoichi Hazama, Keisuke Umakoshi, Akio Ichimura, Shinji Ikari, Yoichi Sasaki,* and Tasuku Ito


Illustration

Four dinuclear complexes, [M2 O2 ( -O)2 (tpen)]2+ and [M2 O2 ( -O)2 (tppn)]2+ (tpen=N,N,N',N' -tetrakis(2-pyridylmethyl)ethylenediamine, tppn=N,N,N',N' -tetrakis(2-pyridylmethyl)propylenediamine; M=Mo ,W), have `basket type' structures similar to those of the edta and pdta analogs. Asymmetric distortion along the Mo-Mo axis of the Mo-R -tppn complex is in the direction opposite to that of the corresponding R -pdta complex. Electronic absorption spectral patterns of the new complexes are generally similar to the corresponding edta complexes. Electronic absorption spectrum of the Mo2 (IV,V) mixed valence state was obtained using spectroelectrochemical techniques. Kinetic parameters of the inversion of the pseudo-gauche conformation of diamine moiety in the tpen complexes are significantly different from those of the edta analogs.

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

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 469-475 (1995) [Vol. 68, No. 2, February, 1995]

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

Structure, Composition, and Vibrational Property of Iodine-Doped Polyvinyl Alcohol Studied by Temperature-Dependent I K-Edge Extended X-Ray-Absorption Fine Structure

Toshihiko Yokoyama, Kentaro Kaneyuki, Hitoshi Sato, Hiroshi Hamamatsu, and Toshiaki Ohta*


Illustration

Temperature dependence of the I K-edge EXAFS of a highly oriented I-PVA film was investigated in order to reveal any local structures around I. It was first demonstrated that the analysis of the EXAFS amplitude, which is associated with the Debye-Waller factor, gives information about the composition ratio of isolated I- , I3- , and I5- .

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 476-480 (1995) [Vol. 68, No. 2, February, 1995]

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

Electrochemical Impedance Study and Characteristics of Polyaniline Film Electrodes

Teruhisa Komura,* Hironobu Sakabayashi, and Koshin Takahashi


Illustration

The impedance analysis of a polyaniline film electrode indicated that the electron exchange between metal and redox sites of the polymer controlled the rate of charge transfer process. A large capacitance in the partially oxidized state is explained in terms of the charge saturation effect associated with the finite thickness.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 481-492 (1995) [Vol. 68, No. 2, February, 1995]

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

Electro-Optical and Hydrodynamic Properties of Synthetic Polyribonucleotides in Solutions as Studied by Electric Birefringence

Masato Tanigawa and Kiwamu Yamaoka*


Illustration

The saturable induced dipole moment ( ; circles) is in fairly good agreement with the theoretical line, which was calculated using a recent Manning theory; it is therefore probably caused by the polarization of condensed counter ions on a polyion, while the unsaturable induced dipole moment may result from polarization of the Debye-Hckel ion-atmosphere.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 493-501 (1995) [Vol. 68, No. 2, February, 1995]

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

Thermoosmosis and Transported Entropy of Water across Hydrocarbonsulfonic Acid-Type Cation-Exchange Membranes

Takashi Suzuki, Keiko Iwano, Ryotaro Kiyono, and Masayasu Tasaka*


Illustration

Solvent transport, Jv , across hydrocarbonsulfonic acid-type cation-exchange membranes was measured for electrolyte solutions under a temperature difference of bulk solutions, Tb , and an osmotic pressure difference, . For ammonium and most alkylated ammonium ions, thermoosmosis occurred toward the cold side, although thermoosmosis across anion-exchange membranes always occurred toward the hot side regardless of the counterions.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 502-505 (1995) [Vol. 68, No. 2, February, 1995]

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

Interactions of Cu2+ and VO2+ Ions with Phosphatidylcholine Vesicular Membranes as Studied by the 1 H NMR Paramagnetic Relaxation Method

Hisao Tanaka,* Harumi Saito, and Hiroshi Kawazura


Illustration

The spin-relaxation effects of the paramagnetic ions Cu2+ and VO2+ on the protons of solvent water and lipids in phosphatidylcholine membranes were observed. VO2+ occupies a binding site closer to the polar N-methyl groups and less accessible, which causes stronger motional restriction to a bound cation, compared with the site occupied by Cu2+ , as shown in the figure below.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 506-511 (1995) [Vol. 68, No. 2, February, 1995]

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

Pressure Effect on the Inter- and Intramolecular Vibrations of Pyrazine Crystal

Masayoshi Maehara, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada


Illustration

The pressure-induced frequency shift of the intermolecular vibrations, the discontinuous variation of the bandwidth of the intramolecular vibrations by pressure, and the calculation of the pressure-induced frequency shift of the intramolecular vibrations indicate that the molecular orientation changes in the pyrazine crystal under about 1 GPa.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 512-518 (1995) [Vol. 68, No. 2, February, 1995]

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

Raman Spectroscopic Study on the Temperature Dependence of the Uncoupled O-D Stretching Band from HDO Molecules in Concentrated Aqueous Zn(ClO4 )2 Solutions

Yasuo Kameda,* Ikuko Sugawara, Ken-ichi Kijima, Takeshi Usuki, and Osamu Uemura


Illustration

The uncoupled O-D stretching Raman bands for aqueous 2 and 4 mol% Zn(ClO4 )2 solutions were observed at 26-95 °C. Band parameters for Zn2+ and ClO4 - -perturbed O-D bands were decided by the double-difference spectroscopic method using a least squares fitting procedure.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 519-527 (1995) [Vol. 68, No. 2, February, 1995]

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

A Heuristic Molecular-Dynamics Approach for the Prediction of a Molecular Crystal Structure

Nobuo Tajima, Takayuki Tanaka, Tomoko Arikawa, Takashi Sakurai, Shoichi Teramae, and Tsuneo Hirano*,


Illustration

An algorithm to predict the structures of molecular crystals has been developed. This algorithm, called a heuristic MD search, efficiently samples possible candidate structures for a crystal from the MD trajectory, as shown in the figure. This algorithm was successfully applied to predicting the crystal structures of CO2 , benzene, and pyrimidine molecules, as test examples.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 528-538 (1995) [Vol. 68, No. 2, February, 1995]

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

Simulation of the Valence X-Ray Photoelectron Spectra of 16 Polymers by the Semiempirical HAM/3 MO Method Using the Model Molecules

Kazunaka Endo,* Chiaki Inoue, Yasuo Kaneda, Masayuki Aida, Naoya Kobayashi, and Delano P. Chong*,


Illustration

The valence XPS of 16 polymers involving fluorine, nitrogen, a glucose unit, and a benzene nucleus and oxygen were simulated by a semi-empirical HAM/3 MO method using the monomer, dimer or trimer models. For example, Figure 1 shows the simulated spectra of poly(tetrafluoroethylene) (PTFE). The theoretical spectra showed good agreement with the spectra of polymers, as observed between 0-40 eV.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 539-546 (1995) [Vol. 68, No. 2, February, 1995]

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

Hydrate Cluster Formation of Diol Compounds in Aqueous Solution

Satoru Takahashi and Nobuyuki Nishi*


Illustration

Hydration to diol compounds in aqueous solution was investigated by the mass spectrometry of the solution (liquid droplets). Stabilities of monomer- and dimer-hydrate clusters of diol compounds in aqueous solution are much lower than those of 1-alkanols. With increasing size of the alkyl group(s), the stability became higher, showing the nature of hydrophobic hydration. Solute-solute association constants are very small, indicating solubilities of diols are higher than those of 1-alkanols.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 547-553 (1995) [Vol. 68, No. 2, February, 1995]

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

Electrical and Optical Properties of -(BETS)2 I3 and -(BEDT-STF)2 I3

Makoto Inokuchi, Hiroyuki Tajima,* Akiko Kobayashi, Toshiaki Ohta, Haruo Kuroda, Reizo Kato, Toshio Naito, and Hayao Kobayashi


Illustration

The reflectance spectra of -(BETS)2 I3 and -(BEDT-STF)2 I3 exhibit the two-dimensional nature of their electronic structures. The spectral analyses reveal that the transverse inter-molecular interaction increases in the order -(BEDT-TTF)2I3< -(BEDT-STF)2I3<-(BETS)2I3 as the S atoms of TTF skeleton are replaced with Se atoms.

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

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 554-558 (1995) [Vol. 68, No. 2, February, 1995]

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

Binuclear Dioxomolybdenum(VI) Complexes of Flexibly-Bridged Hexadentate Tetraanionic Schiff's Bases Derived from Methylene- or Dithio-bis(salicylaldehyde) and S -Methyldithiocarbazate or S -Benzyldithiocarbazate

Mannar R. Maurya,* Deena C. Antony, Sarada Gopinathan, and Changaramponnath Gopinathan*,


Illustration

Binuclear dioxomolybdenum(VI) complexes of the formula [(MoO2 )2 L] have been prepared using flexibly-bridged hexadentate tetraanionic ligands (LH4 ). [(MoO2 )2 L] reacts with monodentate ligands like DMSO, pyridine, and 4-methylpyridine to give monomeric species [(MoO2 )2 L(D)2 ]. These complexes are characterized by elemental analyses and various spectroscoppic techniques.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 559-565 (1995) [Vol. 68, No. 2, February, 1995]

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

Silica Gel-Bonded Cationic Polyelectrolyte with Ferron as Counterion. Application to Preconcentration or Elimination of Trace Metals

Bhim Bali Prasad* and Sonu Sundd


Illustration

Silica gel-bound N-based cationic polyelectrolyte, Poly[N -xylylene-N ,N' -dicyclohexylethylenediammonium dibromide], modified as chelator with ferron as counterion, was studied as sorbent under static and dynamic methods. The sorbent is selective for the retention of Cu2+ , Pb2+ , and Fe3+ from the multi-element samples and is found to be a suitable stable packing material for reagent (buffer) purification.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 566-573 (1995) [Vol. 68, No. 2, February, 1995]

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

Observation of Nuclear Excitation by Electron Transition (NEET) in 197 Au with a Nanosecond Stroboscopic Electron Spectrometer

Atsushi Shinohara,*, Tadashi Saito, Kiyoteru Otozai, Hiromu Fujioka,, and Katsumi Ura,


Illustration

Nuclear excitation by electron transition (NEET) in 197 Au was observed in time spectra of 63-keV electrons measured with a specially designed nanosecond stroboscopic electron spectrometer. The NEET probability was deduced to be P=(5.1±3.6)×10 -5 . This is the third observation of the NEET phenomenon following 189 Os and 237 Np.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 574-580 (1995) [Vol. 68, No. 2, February, 1995]

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

Syntheses and Structural Characterization of Dinuclear and Trinuclear Iron(II) Complexes of Tridentate Thiolic Ligands with an NNS Donor Set

Masahiro Mikuriya,* Takanori Kotera, Fumiya Adachi, Makoto Handa, Masayuki Koikawa,, and Hisashi kawa


Illustration

The crystal structures of iron(II) complexes with 2-[(2-aminoethyl)amino]ethanethiol (HLa ), 2-[(3-aminopropyl)amino]ethanethiol (HLb ), and 2-[[2-(2-pyridyl)ethyl]amino]ethanethiol (HLc ) - [Fe{Fe(La )2 }2 ](ClO4 )2 .CH3 OH ( 1 ), [Fe{Fe(Lb )2 }2 ]Cl2 .2CH3 OH ( 2 ), and [Fe2 (Lc )2 (NO3 )2 ] ( 3 ), respectively - have been analyzed by the single-crystal X-ray diffraction method. The electronic spectroscopic and magnetic properties are discussed in relation to the crystal structures.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 581-589 (1995) [Vol. 68, No. 2, February, 1995]

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

Molecular Structure of Nitro- and Nitrito-Copper Complexes as Reaction Intermediates in Electrochemical Reduction of Nitrite to Dinitrogen Oxide

Nobutoshi Komeda, Hirotaka Nagao, Yoshinori Kushi, Gin-ya Adachi, Masatatsu Suzuki, Akira Uehara, and Koji Tanaka*,


Illustration

Electrochemical reduction of NO2- in the presence of [Cu(H2 O)(tpa)](ClO4 )2 (tpa=tris[(2-pyridyl)methyl]amine) at -0.4 V in H2 O (pH 7.0) catalytically produced N2 O with concomitant evolution of a small amout of NO. Two isomers as intermediates in the NO2- reduction, [Cu(ONO)(tpa)]PF6 and [Cu(NO2 )(tpa)]PF6 , which exist as an equilibrium mixture in solutions, were isolated and their structures were determined.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 590-593 (1995) [Vol. 68, No. 2, February, 1995]

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

Synergic Extraction Equilibrium of Mn(II) with 4,4,4-Trifluoro-1-(2-thienyl)-1,3-butanedione and Neutral Multidentate Ligands, Such as Terpyridine and Tetraphenyldiphosphane Dioxide

Saeko Satake, Satoshi Tsukahara,* and Nobuo Suzuki

Synergic extraction of Mn(II) was examined in novel systems using 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Htta) and a neutral ligand, 2,2' : 6' ,2'' -terpyridine (terpy) or tetraphenyldiphosphane dioxide (tpdpo). Large synergic effects and quantitative extraction of Mn(II) were observed in both extraction systems. Mn(II) was extracted as 1 or 2 , and the equilibrium constants were obtained.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 594-603 (1995) [Vol. 68, No. 2, February, 1995]

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

Analysis of d-d Transitions in [Cr(CN)(NH3 )5 ]2+ as Inferred from Polarized Optical Spectra and Angular Overlap Model Calculations

Akio Urushiyama,* Mutsuyoshi Itoh, and Thomas Schnherr


Illustration

A vibronic analysis of the crystal absorption spectra of [Cr(CN)(NH3 )5 ]Cl(ClO4 ) in the intraconfigurational doublet transition region yielded the confirmed locations of a total of five electronic origins. Including the splittings of the quartet bands, AOM parameters were optimized, which involve a strong -accepter property of CN- (ex(CN)=-900 cm-1 ) and not too much of a strong -antibonding behavior e(CN)=7600 cm-1 .

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 604-609 (1995) [Vol. 68, No. 2, February, 1995]

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

Extraction Behavior of Di- -oxo-bis[oxomolybdenum(V)] with 2-Methyl-5-octyloxymethyl-8-quinolinol

Yuqi Feng, Hisanori Imura,* and Kousaburo Ohashi


Illustration

Binuclear oxomolybdenum(V), Mo2 O42+ , was quantitatively extracted with a new hydrophobic ligand, 2-methyl-5-octyloxymethyl-8-quinolinol (HMO8 Q), in chloroform and isobutyl methyl ketone from a weakly acidic medium. The extracted complex was Mo2 O4 (MO8 Q)2 , which formed such an adduct with trioctylphosphine oxide (TOPO) as Mo2 O4 (MO8 Q)2 (TOPO) in benzene and chloroform.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 610-615 (1995) [Vol. 68, No. 2, February, 1995]

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

Synthesis and Properties of Linear-Type S-Bridged RhIII NiII RhIII Trinuclear Complexes with 2-Aminoethanethiolate (aet) or L -Cysteinate ( L -cys). Crystal Structure of [Ni{Rh(aet)3 }2 ](NO3 )2

Takumi Konno* and Ken-ichi Okamoto


Illustration

The easy reactions of fac (S )-[Rh(aet)3 ] or LLL -fac (S )-[Rh( L -cys-N ,S )3 ]3- with Ni2+ give linear-type S-bridged RhIII NiII RhIII trinuclear complexes, rac -[Ni{Rh(aet)3 }2 ]2+ (rac - 1 ) and LLLLLL -[Ni{Rh( L -cys-N ,S )3 }2 ]4- (LLLLLL - 2 ). The preparation of the optically active or isomer of 1 is achieved by the treatment of - or -[{Rh(aet)3 }4 Zn3 (HO)]5+ with excess Ni2+ . These complexes are characterized by a combination of X-ray diffraction and absorption and CD spectra. Their chemical properties are discussed in comparison with those of the corresponding CoIII NiII CoIII and RhIII CoIII RhIII trinuclear complexes.

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

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 616-619 (1995) [Vol. 68, No. 2, February, 1995]

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

Synthesis and Photochromic Properties of Fulgides with a t -Butyl Substituent on the Furyl- or Thienylmethylidene Moiety

Jitsuo Kiji,* Tamon Okano, Hitoshi Kitamura, Yasushi Yokoyama,*, Shuji Kubota, and Yukio Kurita


Illustration

t -Butyl (R=t -C4 H9 )-substituted furyl (X=O ) and thienyl (X=S ) fulgides were prepared for the first time by the palladium-catalyzed carbonylation of 2-pentyne-2,4-diols as shown in the scheme below. Coloring quantum yields of the fulgides are 0.79 and 0.73, respectively.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 620-624 (1995) [Vol. 68, No. 2, February, 1995]

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

Antioxidant Activities of Aminophenols against Oxidation of Methyl Linoleate in Solution

Misato Iwatsuki, Erika Komuro, and Etsuo Niki*


Illustration

The antioxidant activities of 48 kinds of aminophenols, chromanols, indoles, carbazoles, aromatic amines compounds were assessed against the oxidation of methyl linoleate in solution. Their antioxidant activities were interpreted by both polar and resonance effects. -Tocopherol and related chromanoles were most active.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 625-634 (1995) [Vol. 68, No. 2, February, 1995]

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

Triethylborane-Induced Radical Cyclization of 1-Allyloxy-2-halosilacyclopentane. Stereoselective Synthesis of 1,3,6-Triols Starting from Silacyclobutane

Kozo Matsumoto, Katsukiyo Miura, Koichiro Oshima,* and Kiitiro Utimoto*


Illustration

The treatment of 1-allyloxy-2-bromo-1-phenylsilacyclopentane with n -Bu3 SnH in the presence of a catalytic amount of Et3 B provided 2-oxa-1-silabicyclo[3.3.0]octane, which was converted into 1,3,6-triol by the oxidative cleavage of silicon-carbon bonds with H2 O2 .

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 635-644 (1995) [Vol. 68, No. 2, February, 1995]

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

Synthesis and Molecular Structure of [4][34 ](1,2,3,4,5)Ferrocenophane

Masao Hisatome,* Jun Watanabe, Koji Yamakawa, Kozo Kozawa, and Tokiko Uchida


Illustration

The title compound ( 1 ), a caged pentabridged ferrocenophane, was synthesized and characterized by an X-ray analysis and spectrometry. Both the Fe-Cp distance (1.55 ) and the wavelength of the d-d* absorption band (345 nm) in 1 are smallest among those of ever observed multibridged ferrocenophanes.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 645-653 (1995) [Vol. 68, No. 2, February, 1995]

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

Stereoselective Allylation of 2-Formyl Amides or 3-Oxo Amides

Masahiko Taniguchi, Koichiro Oshima,* and Kiitiro Utimoto*


Illustration

Whereas treatment of 2-methyl-3-oxo amide with allylzinc bromide provided erythro -3-hydroxy-2-methyl-5-hexenamide with high stereoselectivity, allylation with allylsilane in the presence of a catalytic amount of n -Bu4 NF afforded stereoisomeric threo hydroxy amide exclusively.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 654-660 (1995) [Vol. 68, No. 2, February, 1995]

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

Synthesis and Properties of Cationic Organopalladium Complexes. Remarkable Rate Enhancement in Olefin Insertion into the Palladium-Aryl Bond by the Generation of a Cationic Palladium Complex from trans -[PdBr(Ph)(PMe3 )2 ]

Futoshi Kawataka, Isao Shimizu, and Akio Yamamoto*


Illustration

Ionic palladium complexes, trans -[PdPh(solvent)(PMe3 )2 ]BF4 ( 3 ) and trans -[PdPh(py)(PMe3 )2 ]BF4 ( 2 ), have high reactivities toward olefin insertion reactions than neutral complex, trans -PdPh(Br)(PMe3 )2 ( 1 ). Kinetic studies on insertions of olefins into 1 - 3 revealed the importance of creating a vacant site in cationic phenylpalladium complexes.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 661-669 (1995) [Vol. 68, No. 2, February, 1995]

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

Synthesis, Properties, and Structures of 1,2 : 5,6-Bis(ethylenedithio)pyracylene and Its Radical Cation Salts

Hiroyuki Tani


Illustration

1,2 : 5,6-Bis(ethylenedithio)pyracylene ( 2 ) was synthesized as a polyaromatic fused-type donor with two ethylenedithio groups at the periphery. Molecule 2 showed the reversible two low oxidation potentials and was readily oxidized to afford single crystal radical cation salts with hexafluorophosphate (PF6 ||- ) and triiodide (I3 ||- ) by electrocrystallization. The crystal structures of the salts, ( 2 )3 (PF6 )2 and ( 2 )2 I3 , were identified by X-ray diffraction.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 670-672 (1995) [Vol. 68, No. 2, February, 1995]

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

Short Synthesis of (3 S ,4 R )- and (3 R ,4 R )-3-Hydroxy-4-hydroxymethyl-4-butanolides, Two Lactones from Levoglucosenone

Katsuya Matsumoto,* Takashi Ebata, Koshi Koseki, Koji Okano, Hiroshi Kawakami, and Hajime Matsushita


Illustration

(3S ,4R )-3-Hydroxy-4-hydroxymethyl-4-butanolide was easily and stereoselectively synthesized from levoglucosenone (1,6-anhydro-3,4-dideoxy- - D -glycero -hex-3-enopyranos-2-ulose) in two steps and in 64.3% overall yield. The diastereomer, (3R ,4R )-isomer, was also stereoselectively synthesized from levoglucosenone in five steps and in 42.3% overall yield.

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

Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 673-682 (1995) [Vol. 68, No. 2, February, 1995]

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

Solvent Effects on the Solvolysis of p -Nitrobenzyl and 3,5-Bis(trifluoromethyl)benzyl p -Toluenesulfonates

Mizue Fujio,* Toshihiro Susuki, Mutsuo Goto, Yutaka Tsuji, Ken-ichi Yatsugi, Sung Hong Kim, Gamal Abdel-Wahab Ahmed, and Yuho Tsuno


Illustration

Solvolysis rates of p -nitrobenzyl and 3,5-bis(trifluoromethyl)benzyl p -toluenesulfonates were determined in a wide variety of solvents. The solvent effects were analyzed based on the Winstein-Grunwald equation. The application of this equation gave a low m value of 0.4 and a large l of close to unity for both derivatives.

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