Shinji Ikari,
Yoichi Sasaki,*
and
Tasuku Ito
RETRUN to the front page
Copyright (C) 1995 by The Chemical Society of Japan
=============================
Accounts
=============================
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
=============================
Headline Articles
=============================
GO TO the graphical abstract
GO TO the graphical abstract
Shinji Ikari,
Yoichi Sasaki,*
and
Tasuku Ito
=============================
Articles
General and Physical
=============================
GO TO the graphical abstract
Hiroshi Hamamatsu, and
Toshiaki Ohta*
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
Takashi Sakurai,
Shoichi Teramae,
and
Tsuneo Hirano*,
GO TO the graphical abstract
GO TO the graphical abstract
-(BETS)2
I3
and
-(BEDT-STF)2
I3
GO TO the graphical abstract
Toshio Naito,
and
Hayao Kobayashi
=============================
Articles
Analitical and Inorganic
=============================
GO TO the graphical abstract
Sarada Gopinathan,
and
Changaramponnath Gopinathan*,
GO TO the graphical abstract
GO TO the graphical abstract
,
,
GO TO the graphical abstract
Masayuki Koikawa,,
kawa
GO TO the graphical abstract
Yoshinori Kushi,
Gin-ya Adachi,
Masatatsu Suzuki,
Akira Uehara,
and
Koji Tanaka*,
GO TO the graphical abstract
GO TO the graphical abstract
nherr
-oxo-bis[oxomolybdenum(V)] with 2-Methyl-5-octyloxymethyl-8-quinolinol
GO TO the graphical abstract
GO TO the graphical abstract
=============================
Articles
Orgainc and Biological
=============================
GO TO the graphical abstract
Shuji Kubota,
and
Yukio Kurita
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
and
Tokiko Uchida
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
GO TO the graphical abstract
Ken-ichi Yatsugi,
Sung Hong Kim,
Gamal Abdel-Wahab Ahmed, and
Yuho Tsuno
RETRUN to the front page
Copyright (C) 1995 The Chemical Society of Japan
=============================
Accounts
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 403-419 (1995) [Vol. 68, No. 2, February, 1995]
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]
Polymetallic C2 (C2
and C2
H) complexes are prepared by structure expansion of parent metal acetylide complexes, Fp*
-C
C-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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 433-446 (1995) [Vol. 68, No. 2, February, 1995]
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.
=============================
Headline Articles
=============================
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 447-455 (1995) [Vol. 68, No. 2, February, 1995]
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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 456-468 (1995) [Vol. 68, No. 2, February, 1995]
Shinji Ikari,
Yoichi Sasaki,*
and
Tasuku Ito
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.
=============================
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]
Hiroshi Hamamatsu, and
Toshiaki Ohta*
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]
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]
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-H
ckel ion-atmosphere.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 493-501 (1995) [Vol. 68, No. 2, February, 1995]
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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 502-505 (1995) [Vol. 68, No. 2, February, 1995]
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]
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]
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]
Takashi Sakurai,
Shoichi Teramae,
and
Tsuneo Hirano*,
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]
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]
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]
-(BETS)2
I3
and
-(BEDT-STF)2
I3
Toshio Naito,
and
Hayao Kobayashi
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.
=============================
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]
Sarada Gopinathan,
and
Changaramponnath Gopinathan*,
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]
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]
,
,
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]
Masayuki Koikawa,,kawa
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]
Yoshinori Kushi,
Gin-ya Adachi,
Masatatsu Suzuki,
Akira Uehara,
and
Koji Tanaka*,
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]
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]
nherr
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
.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 604-609 (1995) [Vol. 68, No. 2, February, 1995]
-oxo-bis[oxomolybdenum(V)] with 2-Methyl-5-octyloxymethyl-8-quinolinol
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]
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.
=============================
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]
Shuji Kubota,
and
Yukio Kurita
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]
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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 625-634 (1995) [Vol. 68, No. 2, February, 1995]
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]
and
Tokiko Uchida
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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 645-653 (1995) [Vol. 68, No. 2, February, 1995]
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]
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]
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]
(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.
Copyright (C)
1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
68, 673-682 (1995) [Vol. 68, No. 2, February, 1995]
Ken-ichi Yatsugi,
Sung Hong Kim,
Gamal Abdel-Wahab Ahmed, and
Yuho Tsuno
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]
