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Articles
General and Physical
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-Hydroxy Acids in a Carbonate-Hydrogencarbonate Buffer Medium
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Articles
Analitical and Inorganic
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and
Tatsuya Sekine
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-Dodecamolybdophosphate in Aqueous Solutions:
Electrical Conductivity, 31
P NMR, and Crystallographic Studies
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3
-Chloride-Bridged Tripalladium Compounds, [Pd3
(
3
-Cl)2
(HqnS)6
]Cl2
(HqnS = Quinoline-2(1
H
)-thione) and [Pd3
(
3
-Cl)2
(Et2
dtc)2
(PPh3
)2
].C6
H6
(Et2
dtc =
N
,
N'
-Diethyldithiocarbamate)
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and
Megumu Munakata
MM*
-
L
Odd Electron Delocalization onto Aromatic Bridging Ligands in a Paramagnetic Dirhodium Complex and Intermolecular -Stack Interaction in Crystal
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Kunihisa Sugimoto,
Takayoshi Kuroda-Sowa,
and
Megumu Munakata
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Articles
Orgainc and Biological
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Hidetoshi Yamamoto,
and
Eiji Wada
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Takanori Kobayashi,
and
Takao Takeuchi
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Articles
Applied and Materials
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Copyright (C) 2000 The Chemical Society of Japan
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Accounts
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Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 507-514 (2000) [Vol. 73, No. 3, March, 2000]
Recent studies on ultrafast energy transfer at solid/liquid interfaces were reviewed, focusing mainly on photothermal spectroscopy and behavior of hot electrons. Ultrafast relaxation (110-690 fs) was also observed at TiO2 /KSCN (aq) interfaces by the femtosecond transient reflecting grating method.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 515-534 (2000) [Vol. 73, No. 3, March, 2000]
The Cu salts of a series of -acceptors N
,N'
-dicyanobenzoquinonediimines (DCNQIs) are characterized by coexistence of 3d electrons in Cu and p electrons in DCNQI near the Fermi level. This unique feature has provided a lot of interesting solid state properties.
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 535-552 (2000) [Vol. 73, No. 3, March, 2000]
The structure and reactivities of 1,3-dipolar peroxy species represented as X+ -O-O- such as ozone (X = O ), nitroso oxides (X = RN ), carbonyl oxides (X = R2C ), and persulfoxides (X = R2S ) are different depending on the nature of X. These active oxygen species can be classified into two types. The individual features as well as the overviews of their properties are reviewed.
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Articles
General and Physical
=============================
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 553-560 (2000) [Vol. 73, No. 3, March, 2000]
-Hydroxy Acids in a Carbonate-Hydrogencarbonate Buffer Medium
Kinetic evidence indicated the formation of a 1 : 1 complex between hexachloroplatinate(IV) and some neutralized
-hydroxy acids in a carbonate-hydrogencarbonate buffer medium. The complex decomposes to give respective carbonyl compounds via C-C bond cleavage. Platinum(IV) is reduced to platinum(II) in a one-step, two-electron process.
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 561-568 (2000) [Vol. 73, No. 3, March, 2000]
The localized corrosion of Cl- in citrate solution was examined in the absence and presence of oxo-anions. For all examined concentrations of Cl- , the pitting potentials were shifted toward negative values, see Fig. 5. The order of oxo-anions inhibiting effect on the aggresive Cl- ions is: CrO42- > WO42- > MoO42- indicating that CrO4 2- remains the best inhibitor to prevent the pitting corrosion, probably through its ability to repair defects in the oxide film.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 569-573 (2000) [Vol. 73, No. 3, March, 2000]
Multiple metal-rich ion alkali halide (MR-AX) clusters have been produced and characterized for the first time by a newly developed high-pressure laser-vaporization cluster source. We have found the structures of multiple excess electrons and those of metal clusters separated from alkali-halide clusters.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 575-581 (2000) [Vol. 73, No. 3, March, 2000]
The illumination of 2-(diethylcarbamoyl)quinolines induced alkyl-insertion to the C(O)-N bond and five-membered cyclization. 2-(Ethylcarbamoyl)quinoline did not undertake a photochemical change. This could be attributed to an unfavorable orientation of the ethylcarbamoyl substituent for hydrogen-atom abstraction by a ring nitrogen.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 583-587 (2000) [Vol. 73, No. 3, March, 2000]
3-Thiopheneacetic acid was electrochemically oxidized and polymerized on ITO electrodes in a 0.05 mol dm-3 Bu4 NClO4 acetonitrile solution. The resulting poly(3-thiopheneacetic acid) behaved as an n-type semiconductor.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 589-598 (2000) [Vol. 73, No. 3, March, 2000]
Absorption spectra of the singlet- and triplet-excited states of C60
were dependent on the ionization potential of the solvent molecules. The dependence was ascribed to a specific interaction of the C60
-excited states with solvent molecules through donating their -electron density.
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 599-605 (2000) [Vol. 73, No. 3, March, 2000]
RuX2 (ethylene)(pybox) [X = Cl , I, and CF3 SO3 pybox = 2 ,6-bis[(4S )-4-isopropyl-2-oxazolin-2-yl]pyridine]- MAO catalysts have exhibited moderate catalytic activity for both ethylene homopolymerization and ethylene/1-hexene copolymerization. Only a linear polyethylene was obtained if FeCl2 (pybox) was employed under the same copolymerization conditions.
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Articles
Analitical and Inorganic
=============================
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 607-614 (2000) [Vol. 73, No. 3, March, 2000]
A ruthenium aqua complex having quinone ligand [Ru(trpy)(dbq)(H2 O)](ClO4 )2 (dbq = 3,5-di-t-butyl-1,2-benzoquinone ) was prepared. Deprotonation of aqua ligand resulted in the reduction of the complex. The characteristic redox reactions were applied to a unique device for energy conversion from proton gradient to electricity.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 615-622 (2000) [Vol. 73, No. 3, March, 2000]
The lanthanoids and yttrium in eleven rock standard reference materials (GSJ, Igneous rock series) were determined by inductively coupled plasma mass spectrometry after cation exchange pretreatment. The precise and accurate isobaric oxide correction method was successfully accomplished.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 623-630 (2000) [Vol. 73, No. 3, March, 2000]
and
Tatsuya Sekine
Picrate (pic- ) ions enhance the Eu(III) extraction with diamide ( da ) from an aqueous HNO3 solution into benzene very effectively; pic- ions work as counter ions for the [Eu ( da )2 ]3+ cation, instead of NO3 - ions. The anion effect can originate in the hydrophobicity of pic- .
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 631-639 (2000) [Vol. 73, No. 3, March, 2000]
A series of sulfide-bridged di- or trinuclear pyrrolylimido and diazoalkane complexes containing W alone or both W and Rh have been derived from the dinitrogen complex cis -[W(N2 )2 (PMe2 Ph)4 ] and fully characterized by X-ray analyses.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 641-649 (2000) [Vol. 73, No. 3, March, 2000]
-Dodecamolybdophosphate in Aqueous Solutions:
Electrical Conductivity, 31
P NMR, and Crystallographic Studies
The photoreduction processes of
-[PMo12
O40
]3-
(
-PMo12
(0)) to 
-[H4
PMo12
O40
]3-
(
-PMo12
(IV)) are discussed on the basis of the electrical conductivity and 31
P NMR spectra in conjunction with the crystal structures of the
-type two-electron reduced and
-type four-electron reduced species,
-[(i
Pr)2
NH2
]4
[HPMo12
O40
].4H2
O (
1
) (
-PMo12
(II)) and
-[(i
Pr)2
NH2
]3
[H4
PMo12
O40
].2H2
O (
2
) (
-PMo12
(IV)).
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 651-655 (2000) [Vol. 73, No. 3, March, 2000]
3
-Chloride-Bridged Tripalladium Compounds, [Pd3
(
3
-Cl)2
(HqnS)6
]Cl2
(HqnS = Quinoline-2(1
H
)-thione) and [Pd3
(
3
-Cl)2
(Et2
dtc)2
(PPh3
)2
].C6
H6
(Et2
dtc =
N
,
N'
-Diethyldithiocarbamate)
and
Megumu Munakata
Two di-3
-chloride-bridged tripalladium compounds, [Pd3
(3
-Cl)2
(HqnS)6
]Cl2
(
1
) and [Pd3
(3
-Cl)2
(Et2
dtc)2
(PPh3
)2
].C6
H6
(
2
) were synthesized and structurally characterised. The ground state spin multiplicities are triplet, and singlet for
1
and
2
, respectively.
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 657-668 (2000) [Vol. 73, No. 3, March, 2000]
MM*
-L
Odd Electron Delocalization onto Aromatic Bridging Ligands in a Paramagnetic Dirhodium Complex and Intermolecular -Stack Interaction in Crystal
Kunihisa Sugimoto,
Takayoshi Kuroda-Sowa,
and
Megumu Munakata
The odd electron in the RhRh*
orbital of the Rh2
5+
radical is delocalized onto each system of the four bridges to the extent of 9%. Intermolecular interaction arising from -stack packing of the radical in crystal is examined.
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 669-673 (2000) [Vol. 73, No. 3, March, 2000]
Ion association reactions between monovalent polycyclic aromatic cations and anions have been studied through the mobility change in capillary zone electrophoresis. Contribution of aromatic carbon to the ion associability in an aqueous solution was investigated.
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Articles
Orgainc and Biological
=============================
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 675-680 (2000) [Vol. 73, No. 3, March, 2000]
An efficient reaction of epoxides with alcohols, water, acetic acid, acetone and anions such as chloride, bromide, iodide, thiocyanate and nitrate catalyzed with iron(III) trifluoroacetate is described.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 681-687 (2000) [Vol. 73, No. 3, March, 2000]
Hidetoshi Yamamoto,
and
Eiji Wada
Enantiopure diphenylmethylglycinol has been synthesized by a hidantoin route and subsequent optical resolution by a chiral HPLC. It is converted to two new chiral oxazoline ligands, 4,4' -bis(diphenylmethyl)-2,2' -bioxazoline and isopropylidene-2,2' -bis(4-diphenylmethyloxazoline).
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 689-692 (2000) [Vol. 73, No. 3, March, 2000]
A convenient one pot allylation of aldehydes with allylic iodides prepared in situ from allylic alcohols by using trimethylsilyl chloride and sodium iodide proceeds smoothly in the presence of metallic bismuth to afford the corresponding homoallylic alcohols in good yields.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 693-704 (2000) [Vol. 73, No. 3, March, 2000]
For the synthesis of newly designed polymorphismic molecules, an efficient synthetic method for several types of internal and terminal macromonocyclic polyamines as useful building blocks was established.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 705-712 (2000) [Vol. 73, No. 3, March, 2000]
Optically pure bisphosphine oxides were conveniently synthesized by Kolbe electrolytic coupling reaction of carboxylic acids possessing a chiral phosphinoyl group in 60-65% isolated yield. This synthetic approach provides a variety of accesses to optically pure bisphosphine ligands.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 713-719 (2000) [Vol. 73, No. 3, March, 2000]
Reaction of oxiranes with CO2 (1 atm) catalyzed by alkali metal salt quantitatively afforded the corresponding five-membered cyclic carbonates. The reaction proceeded with retention of stereochemistry without loss of optical purity. The direction of ring-opening by aminolysis was controlled by the electron-withdrawing ability of R.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 721-727 (2000) [Vol. 73, No. 3, March, 2000]
Acid-catalyzed condensations of 1-methyl and 1,6-di-t -butylazulenes with 9-anthracenecarbaldehyde led to 9-(1-azulenyl)-10-[(1-azulenyl)methylidene]-9,10-dihydroanthracenes as major products, together with (9-anthryl)di(1-azulenyl)methanes. Hydride abstraction from these hydrocarbons with DDQ afforded stable (9-anthryl)di(1-azulenyl)methyl and (1-azulenyl)[10-(1-azulenyl)-9-anthryl]methyl cations.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 729-737 (2000) [Vol. 73, No. 3, March, 2000]
The treatment of 3 with 2KHSO5 .KHSO4 .K2 SO4 yielded 1,2,4,5-tetrathianes 1 and 2 . Their formation mechanism, conformations in the crystalline state and in solution, and thionation of the side-chain carbonyl groups are reported.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 739-743 (2000) [Vol. 73, No. 3, March, 2000]
The 1,3-dipolar cycloadducts of nitrile oxides with p -benzoquinones were treated with acetic anhydride/sulfuric acid to give hydroquinone diacetates. The base-induced rearrangement products from some of the cycloadducts were treated with acetic anhydride/sulfuric acid to give catechol diacetates and/or hydroquinone diacetates depending on a slight difference in the substituents.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 745-746 (2000) [Vol. 73, No. 3, March, 2000]
Takanori Kobayashi,
and
Takao Takeuchi
Poly[N -(5-carboxyhexyl)pyrrole] coated carbon-fiber electrodes incorporating palladium metal microparticles were prepared. On these film electrodes, the electrocatalytic hydrogenation of organic compounds to the hydrogenated products was investigated.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 747-748 (2000) [Vol. 73, No. 3, March, 2000]
An efficient synthetic strategy for catechol derivatives having a variety of substituents at the 4- and 5-positions was achieved by successive Friedel-Crafts acylation, reduction, and demethylation reactions.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 749-750 (2000) [Vol. 73, No. 3, March, 2000]
The Mizoroki-Heck type reaction of silanols with a 3,3,3-trifluoropropyl group with olefins occurred in the presence of a catalytic amount of Pd(OAc)2 . In addition, the palladium-catalyzed cross-coupling reaction proceeded.
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Articles
Applied and Materials
=============================
Copyright (C)
2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 751-758 (2000) [Vol. 73, No. 3, March, 2000]
Nanometer-sized bimetallic Ni/Pd nanoclusters protected by poly(N -vinyl-2-pyrrolidone) exhibit excellent catalytic properties for the reduction of nitro group to amino group in various nitroaromatic compounds under mild conditions. The alloy particles have an ensemble effect on hydrogenation rate, which is 3-4 times greater than that catalyzed by a monometallic colloidal Pd.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 759-763 (2000) [Vol. 73, No. 3, March, 2000]
TPR experiments using deuterium show that most of the reversibly adsorbed sulfur on catalysts is HS- . The peak at 713 K for Pt-Na2 O/Al2 O3 is attributable to the bridging HS- between PtS and Na2 S particles. This HS- species contributes to dehydrogenation.
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2000 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
73, 765-774 (2000) [Vol. 73, No. 3, March, 2000]
A microporous silica gel was prepared by a sol-gel process in the presence of ethylene glycol (EG) and its oligomers, and pore-formation process was investigated using NMR.
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