Bulletin of the Chemical Society of Japan - Vol. 77, No. 1 (January, 2004)

Bulletin of the Chemical Society of Japan
Vol. 77, No. 1 (January, 2004)

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The Chemical Society of Japan Award for 2002

Web Release Date: January 13, 2004

1-12 On the Reaction Mechanism of “Higher-Order Cuprate”, Alias “Lipshutz Cuprate”
E. Nakamura^* and N. Yoshikai
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Experimental and theoretical studies on the structure and the reactivity of the reagent discovered by Lipshutz, once called “higher-order” cyanocuprate (R₂Cu(CN)Li₂), are reviewed. The studies suggest that a minor reactive species is responsible for the unique reactivity of this cuprate.

The Chemical Society of Japan Award for 2002

Web Release Date: January 13, 2004

13-21 Rhodium-Catalyzed Asymmetric Addition of Organo-Boron and -Titanium Reagents to Electron-Deficient Olefins
T. Hayashi
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The asymmetric addition of B-aryl-9BBN and ArTi(OPr-i)₃ in aprotic solvents proceeded with high enantioselectivity under mild conditions to give the corresponding metal enolates as the 1,4-addition products.

The Chemical Society of Japan Award for Creative Work for 2002

Web Release Date: January 13, 2004

23-41 Time-Resolved Thermodynamic Properties of Intermediate Species during Photochemical Reactions
M. Terazima
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We have been attempting to bridge between the thermodynamics and kinetics by developing experimental methods for the time dependent thermodynamical properties of transient species. Some of the results, in particular applications to reactions of biological proteins, are reviewed.

The Chemical Society of Japan Award for Creative Work for 2002

Web Release Date: January 13, 2004

43-58 Recent Synthetic Advances of Tetrathiafulvalene-Based Organic Conductors
T. Otsubo^* and K. Takimiya
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Various TTF-type electron donors were developed by introducing the one-pot preparation of 1,3-dichalcogenole-2-chalcogenones from terminal alkynes and the formation of heterocyclic rings via transalkylation on a chalcogen atom. The scopes and limitations of these reactions are described in connection with the discovery of unique organic superconductors based on MDT-TSF.

Web Release Date: January 13, 2004

59-72 Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes
K. Komiyama, H. Furutachi, S. Nagatomo, A. Hashimoto, H. Hayashi, S. Fujinami, M. Suzuki,^* and T. Kitagawa
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Copper(I) complexes with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) reacted with dioxygen at low temperature to produce superoxocopper(II) and/or trans-(μ-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness on the terminal nitrogens and the reaction conditions.

Web Release Date: January 13, 2004

73-78 The Effect of NaClO₄ Concentration on the Two-Step Electroreduction of Zn²⁺ Ions in the Presence of Tetramethylthiourea
J. Nieszporek, D. Gugala, D. Sieńko, Z. Fekner, and J. Saba^*
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The two-step reduction of Zn²⁺ ions at the dropping mercury electrode and the dependence on NaClO₄ and tetramethylthiourea (TMTU) concentration was examined. The catalytic activity of TMTU concerns both electron transfer steps and decreases in the order: 1 M NaClO₄ > 0.5 M > 0.1 M.

Web Release Date: January 13, 2004

79-86 A Priori Assessment of the Maximum Possible Entrainment Effect Attainable during Preferential Crystallization. The Case of the Simultaneous Resolution of (±)-Ephedrine and (±)-Mandelic Acid
F. Dufour, G. Perez, and G. Coquerel^*
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The simultaneous resolution of chiral acids and bases by preferential crystallization confirms that the performances of the PC are related to the balance between the minimal ratios of heterochiral versus homochiral interaction energies at (hkl) interfaces and the local supersaturation of the counter enantiomer at those interfaces.

Web Release Date: January 13, 2004

87-93 Spin-Probe Study on the Dynamics and Distribution of Solution Molecules in the Nano-Channel of MCM-41
M. Okazaki,^* K. Toriyama,^* N. Sawaguchi, and K. Oda
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The ESR spectrum of a spin-probe showed that a mixture of 2-propanol and cyclohexane exists as a phase-separated liquid at RT in the nano-channel of MCM-41. The solution becomes homogeneous when the inter-granular space is also filled with the solution.

Web Release Date: January 13, 2004

95-99 Excited High-Spin Quartet (S = 3/2) State of a Novel π-Conjugated Organic Spin System, Pyrene–Verdazyl Radical
Y. Teki,^* M. Kimura, S. Narimatsu, K. Ohara, and K. Mukai^*
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A novel verdazyl radical with a pyrene moiety has been designed and synthesized. The excited quartet state of the intramolecular triplet–radical pair was detected by time-resolved ESR. The photo-induced spin alignment was clarified by a MO calculation.

Web Release Date: January 13, 2004

101-102 Incorrect NICS-Based Prediction on the Aromaticity of the Pentalene Dication
J. Aihara
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Nucleus-independent chemical shift (NICS) values do not always reflect aromaticity. The pentalene dication exhibits large negative NICS values at the two ring centers although it is antiaromatic with a large negative topological resonance energy (TRE).

Web Release Date: January 13, 2004

103-107 Synthesis of Mono- and Tri-Nuclear Ruthenium Carbonyl Complexes Containing the Pyridine-2-thiolato Ligand and Reactivity of a Bis(pyridine-2-thiolato) Chelated Ruthenium Dicarbonyl Complex with a Novel Cobalt-Containing Diphosphine Ligand
F.-E Hong,^* Y.-C. Chang, and S.-C. Chen
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Treatment of a bis(pyridinethiolato) chelated monoruthenium dicarbonyl complex, [Ru(4,6-CH₃-3-CN-py-κN-thiol-κS)₂(CO)₂] 7, with a cobalt-containing didentate phosphine ligand, [Co₂(CO)₄(μ-Ph₂PCH₂PPh₂)(μ-PPh₂C≡CPPh₂)] 8, gave a 8-chelated complexes: [Ru(μ-4,6-CH₃-3-CN-2-S-py)(4,6-CH₃-3-CN-2-S-py-κS)(PPh₂CH₂PPh₂)({μ-PPh₂CH₂PPh₂}Co₂(CO)₄{μ-PPh₂C≡CPPh₂})] 10.

Web Release Date: January 13, 2004

109-113 Surface Tension of Barium Chlorapatite Crystals Grown from Flux
T. Suzuki,^* K. Nakayama, and S. Oishi
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Contact angles of water, formamid, ethylene glycol, and diethylene glycol droplets on Ba₅Cl(PO₄)₃ crystals were observed. The surface tension of the grown crystals was calculated in order to study the relationship between the morphology and the surface tension of the crystal surface.

Web Release Date: January 13, 2004

115-121 Density Functional Studies of [{Mo(η⁵-Cp)(CO)₂}₂(μ-H)(μ-PMe₂)], [{Mo(η⁵-Cp)(CO)₂}₂(μ-PMe₂)]⁻ and [{Mo(η⁵-Cp)(CO)₃}₂]: Do the Metal–Metal Bonds Exist?
F.-E Hong^* and Y.-C. Chang
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Density functional studies of [Mo(η⁵-Cp)(CO)₂]₂(μ-H)(μ-PMe₂) 1 and two closely related compounds reveal that there is no direct metal–metal bond in 1 at its singlet ground state, nor are there unpaired electrons around each metal center.

Web Release Date: January 13, 2004

123-131 Ammonia Absorption on Alkaline Earth Halides as Ammonia Separation and Storage Procedure
C. Y. Liu and K. Aika^*
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MgCl(OH), CaCl₂, and CaBr₂ were found to be applicable as ammonia separation material with Temperature Swing Absorption method between 298 and 473 K at 40 kPa, for the low pressure ammonia synthesis at 1 MPa.

Web Release Date: January 13, 2004

133-138 Separation of Dissolved Aluminum in Neutral/Slightly Basic River Water by Cation-Exchange Chromatography with Fluorometric Detection of the Lumogallion–Aluminum Complex
H. Hara,^* M. Fujiwara, and H. Kamiyama
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The cation-exchange chromatographic separation and fluorometric detection of dissolved aluminum in the Seta River revealed that the main species is Al³⁺, which may be formed mainly from Al(OH)₄⁻. A portion of the dissolved aluminum was adsorbed by the cation-exchange column.

Web Release Date: January 13, 2004

139-145 Intermolecular Phenyl Ligand Transfer of Pt(II) and Pd(II) Complexes with Bidentate Ligand
Y. Suzaki and K. Osakada^*
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Aryl complexes of Pd and Pt react with the chloro complexes of these metals with cod ligand to cause intermolecular exchange of the aryl and chloro ligands. The cod ligand in the chloro complex is essential to promote the smooth ligand transfer.

Web Release Date: January 13, 2004

147-155 Autocatalytic Nitration of Pyrene by Aerated Nitrogen Dioxide in Solution and Comparison with the Nitration on Silica Particles
K. Hasegawa,^* H. Kaneko, and T. Ogawa
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The decay of pyrene in trace water containing acetonitrile by aerated NO₂ showed a sigmoid curve, which is characteristic of a proton-autocatalyzed reaction. The autocatalytic reaction was confirmed by a previous addition of HNO₃ gas, which increased the decay rate and shortened the induction period. Dissociated H⁺ of HNO₃, formed by NO₂ aeration, released by nitration, and added previously, acted as an autocatalyst.

Web Release Date: January 13, 2004

157-164 Synthesis of Allyl Acetals and Their Catalytic Claisen–Cope Rearrangement
K. Nakabayashi, M. Ooho, T. Niino, T. Kitamura, and T. Yamaji^*
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We have synthesized various types of acetals using 3-methyl-3-butenal and alcohols with 2,3-double bonding. These acetals have given corresponding aldehydes after the acid catalytic reaction. We have demonstrated that this reaction proceeds via a Claisen–Cope rearrangement.

Web Release Date: January 13, 2004

165-167 A New Family of 2(3H)-Thiazolone Azines as Precursors to Air-Stable Radical Cations
A. Hammami, H. Cavalié-Kosheiry, and M. Armand^*
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Novel 2(3H)-thiazolone azines having R_F substituents on the 4,4′-positions were efficiently prepared in good yields. The two-step synthesis involves the preparation of N,N′-dialkyl-1,2-hydrazinedicarbothiioamides and their reaction with bromomethyl perfluoroalkyl ketone, resulting in double ring closure.

Web Release Date: January 13, 2004

169-178 6-Nitro-2-benzothiazolyl α-Glucoside and α-Mannoside in β-Selective Glycosylations
T. Hashihayata, H. Mandai, and T. Mukaiyama^*
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Highly β-selective glucosylation and mannosylation with 6-nitro-2-benzothiazolyl glycosides were carried out using a catalytic amount of protic acid in good to high yields.

Web Release Date: January 13, 2004

179-185 Synthesis of [2]- and [3]Rotaxanes by an End-Capping Approach Utilizing Urethane Formation
Y. Furusho, H. Sasabe, D. Natsui, K. Murakawa, T. Takata,^* and T. Harada
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The synthetic procedure for [2]- and [3]rotaxanes by end-capping utilizing urethane formation from alcohols and isocyanates is described.

Web Release Date: January 13, 2004

187-188 Synthesis of 1,2,4-Trithiolanes from Thione S-Oxides and Lawesson Reagent at Room Temperature
K. Okuma,^* T. Shigetomi, S. Shibata, and K. Shioji
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The reaction of thioketone S-oxides with Lawesson reagent (L. R.) in the presence of thiones at room temperature afforded 1,2,4-trithiolanes.

Web Release Date: January 13, 2004

189-193 pH Dependence of Interparticle Coupling for Gold Nanoparticle Assemblies Formation: Electrostatic Attraction and Hydrogen Bonding
C.-H. Su, P.-L. Wu,^* and C.-S. Yeh^*
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FT-IR and ¹³C solid-state NMR were employed to characterize the coexistence of hydrogen bonding and electrostatic force of the close-packed self-assembly forming in the sodium-contained aqueous Au colloidal solutions.