-System Stabilized by Silyl Groups.
Synthesis and Characterization
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-System Stabilized by Silyl Groups.
Synthesis and Characterization
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and
Kohei Uosaki
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and
Shigenobu Funahashi
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-Alkanediammonium Bis(decyl sulfate) Solutions and Their Mixtures
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Kazuhide Tani,
and
Akira Nakamura
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Analitical and Inorganic
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Masahiro Mikuriya,*,
Ryoji Nukada,
Ichiro Hiromitsu, and
Kuninobu Kasuga
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Takeshi Sakurai,*
and
Hideki Masuda
- and
-Zirconium Phosphates
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and
Ken-ichi Okamoto
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Hiroyuki Oshita,
and
Masanobu Hidai*,
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Articles
Orgainc and Biological
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-Hydroxyalkylphosphonates Induced by Fluorides or Relatively Weak Bases
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ro Ojima,*
Masahiko Iyoda,
and
Gaku Yamamoto*,
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and
Toshio Sato
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Koichi Sato,
Kunio Oshima,
Shohei Imamura,
Hiroshi Yamataka,
Tsutomu Asano,
and
Masahito Ochiai*,
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Fumitoshi Kakiuchi,
Airi Yamada,
Naoto Chatani, and
Shinji Murai*
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Articles
Applied and Materials
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Copyright (C) 1998 The Chemical Society of Japan
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Accounts
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Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 1-15 (1998) [Vol. 71, No. 1, January, 1998]
Solid parahydrogen is an excellent medium for matrix-isolation spectroscopy because it allows exceedingly high resolution spectroscopy and because it enables us to spectroscopically study fragment products of in situ photolysis of molecules doped in the matrix.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 17-29 (1998) [Vol. 71, No. 1, January, 1998]
This review describes multi-electron reduction of CO2 catalyzed by metal complexes. Transformation from CO2 to CO on metals smoothly takes place either by acid-base equilibria in protic media or by oxide transfer to CO2 in aprotic ones. Conversion from M-CO to M-C(O)R (M = metal; R = H , alkyl) rather than M-CO2 to M-CO, therefore, is the key process for the multi-electron reduction of CO2 in protic and aprotic media. Besides an activation of CO2 on metals, basic ligands also provide suitable reaction sites for the reductive activation of CO2 without any accompanying C-O bond cleavage. Such activation is utilized in catalytic formation of C2 O4 2- by metal-sulfur clusters.
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Headline Articles
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 31-39 (1998) [Vol. 71, No. 1, January, 1998]
The recently developed versatile imaging technique, surface-enhanced Raman imaging (SERI), was used to produce images of self-assembled monolayers (SAMs) formed from a series of para -substituted thiophenols on evaporated silver films with chemical selectivity.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 41-47 (1998) [Vol. 71, No. 1, January, 1998]
-System Stabilized by Silyl Groups.
Synthesis and Characterization
Octasilyltrimethylenecyclopentene tetraanion tetralithium (
3
) with 8 center/12 electron
-system has been prepared and isolated as orange crystals by the reaction of trimethylenecyclopentene (
2
) with Li in THF. The structure of
3
is a stable, closed-shell supercharged tetraanion, which is stabilized not only by the eight silicon atoms but also by the aromatic cyclopentadienyl anion.
=============================
Articles
General and Physical
=============================
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 49-56 (1998) [Vol. 71, No. 1, January, 1998]
Superconductivity is discussed from the viewpoint of the symmetry breaking with the classical field theory, in terms of the Grassmann algebra. The Nambu representation for the Hamiltonian in question is invariant under the rotation about the z axis in the fictitious spin space, so that the Goldstone theorem suggests the condensation along x or y axis, followed by the massless Goldstone boson which is the supercurrent.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 57-65 (1998) [Vol. 71, No. 1, January, 1998]
The spin-lattice relaxation time either in the superconducting or the normal phases is investigated by the use of the Green's function method. In this case the conduction electrons play a role of the lattice and the interaction mainly arises from the Fermi contact term. The behaviors of electrons and nuclei are both quantized. The coherent terms are summarized in a general fashion at the beginning.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 67-71 (1998) [Vol. 71, No. 1, January, 1998]
and
Kohei Uosaki
Formaldehyde in a sulfuric acid aqueous solution makes the rate of the oxide formation slow. However, the reduction rate of the oxide is not affected by formaldehyde. This kinetic asymmetry is explained by dissociative adsorption of formaldehyde on an oxide-free platinum surface.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 73-78 (1998) [Vol. 71, No. 1, January, 1998]
and
Shigenobu Funahashi
The structure and stability of heptahydrated divalent cations of earlier members in the first transition series were studied. The trend concerning the structural stability strongly depends on the electron configuration. The associative mechanism is possible for the water-exchange reaction on hexahydrated divalent cations of the earlier members.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 79-82 (1998) [Vol. 71, No. 1, January, 1998]
The effect of tertiary phosphine was explored for the dimerization of propene using the nickel-phosphine catalyst system described below in the presence of MeSO3 H and/or Me2 SO4 . The catalyst with PEt3 and PEt2 Ph gave exclusively C6 olefins, and the isomer distribution highly depended upon the kind of tertiary phosphine used.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 83-89 (1998) [Vol. 71, No. 1, January, 1998]
By static light scattering measurements at 25 °C, the micelle of 1-tetradecylpyridinium bromide is found to undergo a salt-induced sphere-rod transition at 0.19 mol dm-3 NaBr. The molecular weight of the rodlike micelles is small, probably because of their low solubility in concentrated NaBr solutions.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 91-94 (1998) [Vol. 71, No. 1, January, 1998]
,
-Alkanediammonium Bis(decyl sulfate) Solutions and Their Mixtures
Micellizations of [+
H3
N(CH2
)n
NH3
+
] (C10
H21
SO4
-
)2
(n = 4
, 6, 8) and their mixtures were studied. The critical micelle concentration (C0
) and the micelle aggregation number (m
) change regularly with increasing n
, while the binding degree (
) of the counter ion remains virtually constant. The mixed systems can be explained by the ideal mixing model.
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 95-98 (1998) [Vol. 71, No. 1, January, 1998]
Surface species which were produced by the reaction between methane and oxygen radical anion O.- on MgO at 298 K were detected by FT-IR. They were identified to be methoxide and weakly adsorbed methanol. These species should be produced through the steps shown in the Figure.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 99-112 (1998) [Vol. 71, No. 1, January, 1998]
Kazuhide Tani,
and
Akira Nakamura
The multiple metal-metal bonds between divalent molybdenum (Mo(II)) ions in dimers and tetramers were investigated theoretically to elucidate possible electronic structures of the d-d conjugated systems. The orbital energy gaps, occupation numbers of natural orbitals (NO), effective bond orders and effective exchange integrals (Jab ) were calculated by ab initio UHF MO and DFT methods.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 113-117 (1998) [Vol. 71, No. 1, January, 1998]
Although only a small amount of saccharides was transported from a neutral-solution cell (Part O) to a 10 mM KOH-solution cell (Part A) across an anion-exchange membrane against their concentration gradients in H2 O, the utilization of MeCN as a cosolvent in the neutral-solution cell significantly facilitated the uphill transport of saccharides.
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Analitical and Inorganic
=============================
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 119-125 (1998) [Vol. 71, No. 1, January, 1998]
Masahiro Mikuriya,*,
Ryoji Nukada,
Ichiro Hiromitsu, and
Kuninobu Kasuga
A chain complex [Ru2 (O2 CCMe3 )4 (nitph)]n (BF4 )n (nitph=2 -phenyl-4,4,5,5-tetramethyl-4,5-dihydro-1H -imidazol-1-oxyl 3-N -oxide) has been prepared. The magnetic moment decreased steadily with decrease of temperature aginst the expectation of ferrimagnetic behavior based on the alternating [S=3/2 (Ru(II,III) dimer)]-[S=1/2 (nitph)] alignment.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 127-134 (1998) [Vol. 71, No. 1, January, 1998]
CsSnCl3 showed a phase transition to a cubic perovskite phase at 379 K, at which point the electronic conductivity increased to ca. 10-3 S cm-1 . CH3 NH3 SnCl3 showed successive phase transitions with the temperature, and at least five phases were confirmed. The electric conductivity of these crystals is governed by the semiconducting property.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 135-140 (1998) [Vol. 71, No. 1, January, 1998]
Takeshi Sakurai,*
and
Hideki Masuda
Cytochrome c553 and a membrane-bound cytochrome b , a subunit of NO reductase were isolated from Alcaligenes xylosoxidans GIFU 1051 and characterized by absorption, MCD and EPR spectroscopies.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 141-148 (1998) [Vol. 71, No. 1, January, 1998]
- and
-Zirconium Phosphates
Tridentate polyamines, N(CH2
CH2
NH2
)3
and N(RNH2
)3
(R=CH2CH2CONHCH2CH2
), react with
- and
-zirconium phosphates to give an intercalated phase in which the amine molecules are fully loaded as an interdigitating monolayer with their flattened molecular planes highly tilted relative to the inorganic layers. On the other hand, although hexadentate polyamine, N(RN(RNH2
)2
)3
, forms a more expanded intercalate from its dilute solution, the longer chain amine can not be intercalated from its concentrated solution, due to the entanglement of dissolved molecules.
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 149-153 (1998) [Vol. 71, No. 1, January, 1998]
The adsorption isotherms of phen and Fe(II)-phen were Langmuir type. Some equilibrium parameters were measured from a region where the adsorption obeyed Henry's law and quantitative features of the adsorption of Fe(II)-phen (1 ppm) were displayed. The effect of co-existence anions on the Fe(II)-phen adsorption was also discussed.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 155-160 (1998) [Vol. 71, No. 1, January, 1998]
A novel hexanuclear eight-coordinate complex, [Zr6
(OH)8
(OCH3
)4
(Ph2
CHCOO)12
].2CH3
CN, has been prepared. The six zirconium ions are arranged in apices of an octahedron with eight syn
-syn
bridging carboxylato, eight 
3
-hydroxo, four monodentate carboxylato, and four methoxo groups.
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 161-166 (1998) [Vol. 71, No. 1, January, 1998]
Complexation between B(OH)3 and triethanolamine (H3 L) gives L-B and HL-B(OH) in aqueous solution. Both complexes have a tetrahedral structure around the boron atom, having a boron-nitrogen bond. We believe that this is the first evidence demonstrating the existence of a stable boron-nitrogen bond in aqueous solution.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 167-173 (1998) [Vol. 71, No. 1, January, 1998]
Potassium salts of cobalt(III) and manganese(III) complexes, K[CoL(py)2 ].2EtOH.MeOH 1 and K[MnL(py)2 ].py 2 , have been prepared, where H4L=1,2 -bis(2-hydroxybenzamido)benzene and py=pyridine . 1 and 2 assume an extended one-dimensional and three-dimensional structures due to an electrostatic cation-anion interaction, respectively.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 175-181 (1998) [Vol. 71, No. 1, January, 1998]
and
Ken-ichi Okamoto
Two types of S-bridged polynuclear complexes, [Pd{Co(aet)2 (en)}2 ]Cl4 ( 2 ) and [PdCl2 {Co(aet)2 (en)}]Cl ( 3 ), were produced by reacting [Ni{Co(aet)2 (en)}2 ]Cl4 ( 1 ) with [PdCl4 ]2- in two distinct ratios. 2 was readily converted to 3 by the reaction with [PdCl4 ]2- , while the conversion of 3 to 2 was achieved by reacting 3 with 1 .
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 183-190 (1998) [Vol. 71, No. 1, January, 1998]
Hiroyuki Oshita,
and
Masanobu Hidai*,
The aminocarbene-diazoalkane complexes [MX2 (NN=CMePh){=C(Me)NHBut }(PMe2 Ph)2 ] (M=Mo , W; X=Cl , Br) and the bis(isocyanide)-diazoalkane complex [WCl(NN=CMePh)(CNBut )2 (PMe2 Ph)2 ](OTf) were prepared from diazoalkane-isocyanide complexes [MX2 (NN=CMePh)(CNBut )(PMe2 Ph)2 ] derived from bis(dinitrogen) complexes [M(N2 )2 (PMe2 Ph)4 ].
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Articles
Orgainc and Biological
=============================
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 191-198 (1998) [Vol. 71, No. 1, January, 1998]
A principal component analysis of topological parameters (D
, Dv
, 0
, 1
, 1v
, IC, SIC, CIC, W
,
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 199-207 (1998) [Vol. 71, No. 1, January, 1998]
The electrochemical oxidation of 1,3-dimethylxanthine has been found to proceed in 4e, 4H+ EC reaction. The decay of the UV-absorbing intermediate has been monitored and products have been characterized. A tentative mechanism for oxidation is suggested.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 209-219 (1998) [Vol. 71, No. 1, January, 1998]
-Hydroxyalkylphosphonates Induced by Fluorides or Relatively Weak Bases
Treatment of
-hydroxyalkylphosphonates with a fluoride ion or relatively weak bases gave the corresponding olefins in good yields. It was found by the reaction using threo
- and erythro
-isomers (R1=Me
, R2
, R3=H
, Ph) that the present olefination proceeds stereospecifically in a manner of syn
-elimination.
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 221-230 (1998) [Vol. 71, No. 1, January, 1998]
ro Ojima,*
Masahiko Iyoda,
and
Gaku Yamamoto*,
The catalytic partial hydrogenation of the 5,10-dimethyl-6,8-bisdehydro[13]annulenone using Pd-BaSO4 afforded the 5,10-dimethyl[13]annulenone. This is the first example of a monocyclic non-dehydro annulenone derivative larger than tropone which was found to be atropic.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 231-242 (1998) [Vol. 71, No. 1, January, 1998]
and
Toshio Sato
A partical method has been developed to introduce the desired substituents at both bridgeheads of a bicyclo[2.2.2]oct-5-en-2-one. A formal total synthesis of (±)-modhephene and that of (±)-isocomene have been accomplished starting from the resulting bicyclic compounds through an oxa-di--methane rearrangement.
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 243-257 (1998) [Vol. 71, No. 1, January, 1998]
Koichi Sato,
Kunio Oshima,
Shohei Imamura,
Hiroshi Yamataka,
Tsutomu Asano,
and
Masahito Ochiai*,
In-plane vinylic SN 2 mechanism for the reaction of (E )-1-decenyl(phenyl)iodonium ion with Cl- , Br- , and I- is established from various kinetic and product studies.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 259-272 (1998) [Vol. 71, No. 1, January, 1998]
The chiral and stereoselective total synthesis of novel cerebrosides isolated from starfish, acanthacerebroside A and astrocerebroside A, is described. The phytospphingosine moieties were prepared by a coupling reaction of dialkylmagnesium reagents with a chiral epoxide intermediate, which was synthesized from l -quebrachitol.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 273-283 (1998) [Vol. 71, No. 1, January, 1998]
Ion-molecule reactions of CH5 + , C2 H5 + , and C3 H5 + with five monosubstituted benzenes carrying a carbonyl group (PhCOX: X=H , CH3 , C2 H5 , Ph, COPh) have been studied using an ion-trap type of GC/MS at a low CH4 pressure. The reaction mechanisms are discussed based on product ion distributions and potential-energy diagrams.
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1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 285-298 (1998) [Vol. 71, No. 1, January, 1998]
Fumitoshi Kakiuchi,
Airi Yamada,
Naoto Chatani, and
Shinji Murai*
Transition-metal catalyzed intramolecular C-H/olefin coupling reactions of 1,5- and 1,6-dienes having a nitrogen-containing heteroaromatic ring took place in a highly regioselective manner to give corresponding 5- and 6-membered carbocycles, respectively.
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Articles
Applied and Materials
=============================
Copyright (C)
1998 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
71, 299-303 (1998) [Vol. 71, No. 1, January, 1998]
Reaction between Zn/Al-LDH carbonate and Na2 HPO4 in a suspension system was investigated. A sodalite-type sodium zincophosphate with a small amount of Al atoms incorporated was obtained. The product has a quite similar structure to that of the pure sodalite-like sodium zincophosphate, but showed an improved thermal stability.
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