bluuebunny/crossref_metadata_2025 huggingface dataset:
Photochemical Magnetic Field Effects of 4-Methyl-2-quinolinecarbonitrile
Authors: Hata Norisuke , Nishida Naoya
Published: July 2006

The irradiation of 4-methyl-2-quinolinecarbonitrile 1 in ethanol or cyclohexane resulted in the formation of 2-(1-hydroxyethyl)-4-methylquinoline 2 or 2-cyclohexyl-4-methylquinoline 3 in the yield of ca. 48 or 65%. The effects of an external magnetic field upon the photosubstitution reaction were investigated in either the absence or presence of 1,3-pentadiene (triplet quencher). In the case of the photosubstitution reaction (1→2) in ethanol, the chemical yield of 2 increased quadratically with an increase in the field strength (magnetic field effect due to Δg mechanism) and it also showed a minimum at approximately 1.1T (magnetic field effect due to HFI-J mechanism). The addition of 1,3-pentadiene caused a complete disappearance of the Δg magnetic field effect. Thus, the formation of 2 at a zero field was concluded to occur from the S1-state via the singlet hydrogen-bonded radical pair. In the case of the photosubstitution reaction (1→3) in cyclohexane, the chemical yield of 3 decreased steeply upon the application of a magnetic field 40m T (magnetic field effect due to HFI mechanism) and a further increase in the field strength resulted in a quadratic increase in the yield (magnetic field effect due to Δg mechanism). Neither an HFI nor a Δg magnetic field effect was observed in the presence of 1,3-pentadiene. The reaction was thus concluded to proceed from the S1 and T1 states via the singlet and triplet radical pairs. Reaction mechanisms deduced from the external magnetic field effects were consistent with the results of Stern-Volmer analyses.
The Decomposition of t-Butyl Heptafluoroperoxybutyrate in Aromatic and Aliphatic Solvents
Authors: Sawada Hideo , Hagii Hidehiko , Aoshima Kazuyoshi , Yoshida Masato , Kobayashi Michio
Published: July 2006

Kinetical studies and products analyses of the thermal decomposition of t-butyl heptafluoroperoxybutyrate (TBH) in benzene, octane, nitrobenzene, pyridine, and methoxybenzene have been carried out. In benzene and octane, the decomposition appears to be entirely a radical process. In nitrobenzene and pyridine, the reactions are found to give ionic decomposition products exclusively. On the other hand, the decomposition of TBH in methoxybenzene is characteristic of mixed ionic and radical cleavages.
Internal Energy Distributions of NH(A3II). An Application of Phase Space Theory to the Electron-impact Dissociation
Authors: Tokue Ikuo , Ito Yoshio
Published: July 2006

Internal energy distributions of NH(A) produced by electron impact on NH3, HN3, and HNCO are compared with those predicted by use of the phase space theory based on the method of Light and Pechukas. The values predicted under conservation of energy and total angular momentum are found to be inconsistent with the experimental results. The observed values are well simulated via the introduction of a nonstatistical bias by representing the selective coupling between the reaction coordinate and the rotational modes of the products. The dynamics for formation of NH(A) is discussed.
Preparation and Stereochemistry of Cobalt(III) Complexes Containing (3S,8S)-3,8-Dimethyl-1,1,10,10-tetraphenyl-4,7-diaza-1,10-diphosphadecane or (4S,9S)-2,4,9,11-Tetramethyl-5,8-diaza-2,11-diphosphadodecane (SS-Me2-mm-PNNP). Molecular Structure of (+)589-Λ-cisβ-[Co(acac)(SS-Me2-mm-PNNP)](ClO4)2·H2O (acac=C5H7O2−)
Authors: Atoh Masamichi , Kashiwabara Kazuo , Fujita Junnosuke
Published: July 2006

Two new optically active quadridentate phosphine ligands, (3S,8S)-3,8-dimethyl-1,1,10,10-tetraphenyl-4,7-diaza-1,10-diphosphadecane(SS-Me2-pp-PNNP) and (4S,9S)-2,4,9,11-tetramethyl-5,8-diaza-2,11-diphosphadodecane(SS-Me2-mm-PNNP) and their cobalt(III) complexes, trans-[CoCl2(SS-Me2-pp- or SS-Me2-mm-PNNP)]+, Λ-cisβ-[Co(acac)(SS-Me2-pp-PNNP)]2+ (acac=2,4-pentanedionate ion), Λ-cisβ-[Co(CO3)(SS-Me2-pp-PNNP)]+, and Δ- and Λ-cisβ-[Co(acac)(SS-Me2-mm-PNNP)]2+ were prepared and characterized. The molecular structure and the absolute configuration of (+)589-Λ-cisβ-[Co(acac)(SS-Me2-mm-PNNP)](ClO4)2·H2O were determined by X-ray analysis. Crystal data; monoclinic, C2, a=28.274(4)Å, b=9.266(1)Å, c=11.0901(9)Å, β=92.97(1)°, V=2901.6(5)Å3, and Z=4. Three five-membered chelate rings in the complex form distorted gauche (δλλ) conformations, and the methyl group on carbon of the apically linked chelate ring takes an axial disposition. Stereochemistry of all the complexes was discussed on the basis of the NMR, absorption and CD spectra.
Structural Studies of Thiocyanato and Isothiocyanato Cobalt(III) Complexes Ligating Diamine-N,N′-polycarboxylates
Authors: Kato Yoshikiyo , Isago Hiroaki , Ogino Hiroshi , Toriumi Koshiro , Ito Tasuku
Published: July 2006

Crystal and molecular structures of NH4[Co(NCS)(hedtra)]·H2O and K[Co(SCN)(edtra)]·1.5H2O have been determined by single-crystal X-ray analyses, where hedtra3− and edtra3− denote N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetate and ethylenediamine-N,N,N′-triacetate ions, respectively. Crystal data are as follows: For the former species, triclinic, space group P1, a=7.477(2)Å, b=9.135(2)Å, c=6.899(1)Å; α=84.37(2)°, β=107.31(2)°, γ=108.35(2)°, V=427.0(2)Å3, Z=1; for the latter species, monoclinic, space group P21/a, a=15.288(2)Å, b=7.059(1)Å, c=14.373(2)Å, β=107.55(1), V=1479.0(4)Å3, Z=4. It has been proved unequivocally that the former species contains N-bonded SCN− ligand and the latter species, the S-bonded ligand. Coordination geometry around the cobalt atom in each species deviates considerably from the regular octahedron, so that a very open space is created around the Co–NCS or Co–SCN moiety. This structural feature may be associated with the facile formation of the novel S-bonded species.
Studies on Mixed Chelates. XIV. Influences of Solvent Polarity, and of Substituent Groups in β-Diketonate Ligands, on the Electronic Spectra of 5-Coordinated Mixed Copper(II) Chelates in Organic Solutions
Authors: Fukuda Yutaka , Yasuhira Mayumi , Sone Kozo
Published: July 2006

Several chelates of copper(II), Cu(tmen)(dike)X, were newly obtained where tmen=N,N,N′,N′-tetramethylethylenediamine, dike= a β-diketonate ion, and X−= a halide or pseudohalide anion. These complexes exist as 5-coordinated species, with axially coordinated X−, in nonpolar solvents. In more polar solvents, they are ionized according to the solvent polarity, and form the following equilibrium mixtures:

[Cu(tmen)(dike)X]\ightleftharpoons[Cu(tmen)(dike)]++X−

5–coordinated 4–coordinated(solvated, tetragonal)

This equilibrium is controlled by (a) the strengths of acceptor and donor properties of the solvent, which can be expressed by its polarity factor (Pf), i.e., a linear combination of the donor number and acceptor number of the solvent, and (b) the changes of the ligand field strength of dike caused by the electron-withdrawing and -releasing properties of its α-substituent groups.
CO2 Laser-induced Decomposition of 1,1,2-Trichloroethane
Authors: Ogura Hiroo
Published: July 2006

CH2ClCHCl2 was photolyzed with a focusing geometry using the P(24) line of the 10.6 μm CO2 band (940.6 cm−1). The final products of neat photolysis were cis- and trans-CHCl=CHCl, CH2=CCl2, CH2=CHCl, CH≡CCl, CH≡CH, and C4H2. The relative yield of CH2=CCl2 in particular was strongly dependent on CH2ClCHCl2 pressure and sensitive to the addition of H atom containing molecules. A series of diagnostic experiments shows that the dichloroethene isomers are formed by three different processes, i.e., infrared multiphoton decomposition, collision-induced decomposition, and radical chain reaction. Infrared mulitiphoton decomposition and collision-induced decomposition give rise to cis- and trans-CHCl=CHCl predominantly, while the radical chain reaction generates the dichloroethene isomers in comparable amounts at high reactant pressures, the most probable initiation step being the C–Cl bond-scission reaction of the parent molecule. Formation mechanisms for other minor products are also discussed.
Spectrophotometric Determination of Rhodium(III) and Iridium(III) with 3-Hydroxy-2-methyl-1,4-naphthoquinone 4-Oxime
Authors: Shravah Kamini , Sindhwani S K
Published: July 2006

Rhodium(III) and iridium(III) form 1:3 and 1:2 (metal:ligand) complex, respectively with 3-hydroxy-2-methyl-1,4-naphthoquinone 4-oxime (HMNQM). The complexes are soluble in 20% ethanol. The reagent has been used for the spectrophotometric determination of Rh(III) and Ir(III). The optimum ranges of concentration for the determination of Rh(III) and Ir(III) are 0.27–5.24 and 1.51–15.85 over the pH range 5.0–7.5 and 5.3–8.0, respectively. The Sandell sensitivities for the determination of Rh(III) and Ir(III) are 0.0042 and 0.015 μg cm−2, respectively. The determinations have also been carried out in the presence of foreign ions.
Studies on Double Malonates. II. Potassium Rare Earth Malonates, K5Ln(C3H2O4)4 (Ln=Gd–Ho or Y)
Authors: Nabar Mahadeo Anant , Jukar Bharat Nilkanth
Published: July 2006

Double malonates of some of the rare earths with potassium having formula K5Ln(C3H2O4)4 were synthesized. The lattice parameters of the compounds were determined by X-ray powder diffractometry. Infrared absorption spectroscopy was employed to throw some light on the nature of Ln–O bonding, while the thermoanalytical techniques were made use of in proposing the thermal decomposition mechanism of some of the double malonates.
Effects of Solvents and pH on the Spectral Behavior of 2-(p-Aminophenyl)benzimidazole
Authors: Mishra Ashok Kumar , Dogra Sneh Kumar
Published: July 2006

The absorption and fluorescence spectra in different solvents and at various pH have indicated that monocation and dication of 2-(p-aminophenyl)benzimidazole (PBNH2) are formed by protonating first the tertiary amine nitrogen atom and then the amino group, both in S0 and S1 whereas the monoanion in S0 is obtained by deprotonating the imino group but in S1 it is formed by deprotonating the amino group. Dianion at H–15 in S1 is obtained by deprotonating the amino and then imino group.
Extraction Chromatographic Separation of Uranium (VI) with Amberlite LA-1 from Malonic Acid
Authors: Narayanan Prakash , Khopkar S M
Published: July 2006

Uranium(VI) was extracted between pH 2.5 to 6.0 from 0.01 mol dm−3 malonic acid on a column of silica gel with Amberlite LA-1 as the extractant. It was stripped from the column with 1–2 mol dm−3 of hydrochloric, sulfuric, and nitric acids. Uranium(VI) was separated from alkali, alkaline earths, manganese, iron, cobalt, nickel, zinc, yttrium, lanthanum, cerium in binary mixtures by exploiting the difference in the pH of formation of malonato complexes. Uranium was separated from zirconium, hafnium, thorium, scandium, and titanium by taking its advantage of stability of chloro or sulfato complexes. The method was tested for the standard reference rock samples.
Thermal Studies of 1,2-Propanediamine Complexes of Zinc(II) and Cadmium(II) in the Solid Phase
Authors: Ghosh Ashutosh , De Goutam , Ray Chaudhuri Nirmalendu
Published: July 2006

[ML3]X2·nH2O, where M=ZnII and CdII; L=1,2-propanediamine; X=Cl−, Br−, 0.5SO42−, and 0.5SeO42− and n=1, 1.5, and 2, have been synthesized and their thermal investigations carried out. ZnL1.5Cl2, CdL1.5X2 (X=Cl− and Br−), and CdLX2 (X=Cl−, 0.5SO42−, and 0.5SeO42−) have been synthesized pyrolytically in solid state from their parent diamine complexes. These ML1.5X2 complexes are expected to exist as [ML3][MX4]. Only [CdL3][CdBr4] species has been synthesized from solution. Syntheses of ZnLCl2, CdLCl2, and CdLBr2 from solution have also been reported. IR spectra suggest that symmetry of the chelate ring in mono (diamine) complexes is lowered in comparison to the other complexes. ML1.5Cl2 show isomorphism with each other. Thermal stability sequence of [ML3]X2 (X=Br−, 0.5SO42− and 0.5SeO42−) is SO42−<SeO42−≤Br−. [ZnL3]X2 and ZnLX2 appear thermally more stable than those of cadmium complexes. All these complexes are thermally less stable than those of 1,2-ethanediamine complexes reported by us earlier.
Über die Reaktion von Harnstoff mit Ammoniumhydrogenamidophosphat unter dem Atmosphärendruck
Authors: Shimasaki Choichiro , Hara Mitsunari
Published: July 2006

Die Reaktion von Harnstoff mit Ammoniumhydrogenamidophosphat (NH4HPO3NH2) im Schmelzzustand unter dem Atmosphärendruck ergibt, daß die Bildung des Guanidinumions (GH+) zusammen mit dem Phosphation bei ca. 160 °C die maximale Hitze, und nach 7 Stunden die maximale Ausbeute erreicht. Aus IR Spektren und 31P NMR-Spektren von Reaktionsgemischen und der Entwicklungsbetrag des Ammoniakgases wurde keine Zwischenprodukte, wie Ammoniumureidophosphat, aufgestellt. Die frühere Hauptreaktion der Bildung von GH+ ist das Deamidieren von NH4HPO3NH2. Die gebildete GH+ und das Phosphation bilden mit zunehmender Reaktionstemperatur jeweils die Ringverbindungen wie Triazinverbindungen und die Polmerisaten wie Pyro-, Tripoly-, und Metaphosphat. Das aus NH4HPO3NH2 isolierende Ammoniak unterdrückt die Zersetzung von Harnstoff zu Cyansäure und befördert die Transition zu Cyanamid. Die Bildung von GH+ ist von der Reaktion von Cyanamid mit NH4+ abhängig.
The Reaction of 5-Cyano- and 5-Methoxycarbonyl-7-oxabicyclo[2.2.1]hept-2-enes with Chlorotrimethylsilane/Sodium Iodide Reagent
Authors: Kibayashi Takao , Ishii Yasutaka , Ogawa Masaya
Published: July 2006

Reactions of 5-cyano- and 5-methoxycarbonyl-7-oxabicyclo[2.2.1]hept-2-enes with a chlorotrimethylsilane/sodium iodide reagent in acetonitrile gave 2-furanpropanenitrile and 5-methoxycarbonyl-1,3-cyclohexadiene in good yields, respectively.
Optical Resolution of 3a,4,7,7a-Tetrahydro-4,7-methano-1H-indene Derivatives
Authors: Ito Toshio , Okamoto Yoshio , Matsumoto Takeshi
Published: July 2006

(1RS,3aRS,4RS,7SR,7aSR)-3a,4,7,7a-Tetrahydro-4,7-methano-1H-inden-1-ol was resolved kinetically and its C-1 epimer was resolved chromatographically. Absolute configurations of these resolved compounds were determined.
Phase Diagrams in Binary Systems of Octafluoronaphthalene and Polynuclear Aromatic Compounds
Authors: Miyagishi Shigeyoshi , Isomi Akira , Iwata Mayumi , Asakawa Tsuyoshi , Nishida Morie
Published: July 2006

Solid-liquid phase diagrams were obtained for binary mixtures of octafluoronaphthalene with six polynuclear aromatic compounds, pyrene, phenanthrene, naphthalene, 1,5-naphthylenediamine, anthracene, and phenothiazine, and for mixtures of naphthalene and pyrene. The first four systems all formed well-defined 1:1 molecular complexes with congruent melting points.
NMR Spectra of Substituted 2-(2-Nitrovinyl)thiophenes
Authors: Satonaka Hajime , Watanabe Michio
Published: July 2006

1H and 13C NMR spectra are reported for substituted 2-(2-nitrovinyl) thiophenes. The proton chemical shifts and coupling constants were correlated closely with those of methyl trans-3-(5-substituted 2-thienyl) acrylates. We have found that the additivity rule for 13C chemical shifts of simple substituted thiophenes is applicable to the shifts of the ring carbons in substituted 2-(2-nitrovinyl) thiophenes.
Bromochlorination of Conjugated Dienes with Dichlorobromate(1-) Ion
Authors: Negoro Takeshi , Ikeda Yoshitsugu
Published: July 2006

The reactions of some conjugated dienes with tetrabutylammonium dichlorobromate (1-) (1) were found to give the bromochloroalkenes in good yields, 1,2-addition predominating. Appreciable anti-Markownikoff adduct was obtained from 1,3-butadiene. An AdEC2-type mechanism is suggested.
Possible Interpretation of Inactivity of Novel Gramicidin S Analogs by CD Spectral Analysis of Tetrapeptide Derivatives Related to the Analogs
Authors: Sato Kazuki , Nagai Ukon , Tamaki Makoto
Published: July 2006

CD spectral analysis of chromophoric derivatives of tetrapeptides related to the β-turn part of [d-Val1,1′]-and [d-Val1,1′, l-Phe4,4′]-gramicidin S indicated that they had very low preference for β-turn formation. The results suggested that neither analog could take gramicidin S-like β-sheet conformation. It seems noteworthy that the side-chain bulkiness of the 4th amino acid of a tetrapeptide affects the stability of β-turn.
Further Evidence for the Regioselectivity Rules in Nucleophilic Aromatic Photosubstitution
Authors: Mutai Kiyoshi , Nakagaki Ryoichi
Published: July 2006

In order to assess the validity of our regioselectivity rules for nucleophilic aromatic photosubstitution, 4-nitronaphthyl ethers were designed and their photochemical behavior was studied by applying frontier molecular orbital theory. The results provide supporting evidence for our rules.
The Reaction of Azulene with Nitroethene. A New Route to 2-(1-Azulenyl)ethanamines
Authors: Kurokawa Shinji , Anderson Arthur G.
Published: July 2006

Azulene and guaiazulene react with nitroethene to form substitution products having 2-nitroethyl, 2,4-dinitrobutyl, or 2-nitroethenyl groups at the 1(3)-position in low yields. The presence of formic acid prevented the formation of the dinitrobutyl compound, and increased the yield of the 2-nitroethyl derivative. A reaction course leading to these products is proposed. Reduction of 1-(2-nitroethyl)azulene and 1-(2-nitroethyl)guaiazulene gave the corresponding amine compounds in good yields. This two-step process provides a new, improved route to 2-(1-azulenyl)ethanamines having a primary amino group. The amine products, like related biogenic amines, inhibited the contraction of smooth muscle.
A CIDEP Study of the Addition of Trialkylsilyl Radicals to Substituted p-Benzoquinones
Authors: Craw Marjory T , Alberti Angelo , Depew M Catherine , Wan Jeffrey K S
Published: July 2006

Evidence has been obtained through the combined ESR and CIDEP techniques for the two distinct pathways in which trialkylsilyl radicals add to substituted p-benzoquinones via the carbonyl oxygen as well as the ring carbon–carbon double bonds. The results represent the first observation of CIDEP from organic radicals containing an organosilyl group in solution.
Promotion of Dehydrazination by Nitrobenzenesulfonyl Group from Phosphorus-hydrazone Adducts
Authors: Yamashita Mitsuji , Takeuchi Jun , Nakatani Kaname , Oshikawa Tatsuo , Inokawa Saburo
Published: July 2006

Dehydrazination of adducts of phenylsulfonylhydrazones and phosphorus compounds was promoted by a nitro substituent on the ring to afford derivatives of a phosphine oxide and phosphonates.
Crystal Structure of Binuclear Copper(II) Complex with 3-Ethyl-2-pyridone and Magnetism of Its Homologues
Authors: Nishida Yuzo , Kida Sigeo
Published: July 2006

The crystal structure of bis(N,N-dimethylformamide)tetrakis(3-ethyl-2-pyridonato)dicopper(II) was determined by X-ray diffraction method. Crystal data: Space group P21/n(monoclinic), a=9.906(1), b=13.494(3), c=14.029(2) Å, β=103.81(1)°. The crystal consists of centrosymmetric binuclear units in which two copper(II) ions are linked by four pyridonate anions similarly to copper(II) acetate monohydrate. The Cu–Cu distance is 2.55 Å. The cryomagnetic data revealed that −2J values are in the range 360–405 cm−1 for the series of complexes.
Sulfur-Extrusive Rearrangement of α-Acylthio Ester by Lithium Amide
Authors: Tsuzuki Kazuo , Akeyoshi Masaharu , Omura Satoshi
Published: July 2006

α-Acylthio esters readily undergo facile rearrangement to give β-keto esters on treatment with lithium amide at −78°C. Thiolactone 3, a key intermediate for thiolactonic antibiotics, was synthesized by utilizing the rearrangement.
Intramolecular [3++2] Cycloaddition of 2-Alkenyloxy-1-naphthaldehyde Oximes
Authors: Shimizu Tomio , Hayashi Yoshiyuki , Teramura Kazuhiro
Published: July 2006

The thermal treatment of the mixture of 2-alkenyloxy-1-naphthaldehydes and hydroxylamine hydrochloride in ethanol gave intramolecular [3++2] cycload-ducts, 1,3a,4,11c-tetrahydro-3H-naphtho[1′,2′: 5,6]pyrano[4,3-c]isoxazole hydrochlorides.
Alteration of Reaction Course in Thermolysis of cis-Diethylbis(tertiary phosphine)palladium(II) from Reductive Elimination to β-Elimination Process Induced by Addition of Tertiary Phosphine Ligand
Authors: Ozawa Fumiyuki , Kurihara Kunihiko , Yamamoto Takakazu , Yamamoto Akio
Published: July 2006

Addition of tertiary phosphine to a solution containing cis-diethylbis(tertiary phosphine)palladium(II) alters thermolysis course of the complex from reductive elimination process liberating butane to β-hydrogen elimination process in which ethane and ethylene are released. Study with a deuterium-labeled ethyl complex indicates involvement of an internal metalation process.
Optical and Magnetic Properties of Alkali-(18-Crown-6)-TCNQ Salts
Authors: Nakayama Hideyuki , Ishii Kikujiro
Published: July 2006

Absorption spectra, ESR and static susceptibility were measured on TCNQ salts which incorporate Na+- or K+-(18-crown-6) as the cation unit. Results indicate that charge-transfer interaction between TCNQ anions is weak in the Na+ salt, whereas it is very strong in the K+ salt.
Delayed Fluorescence in Mixed Crystals Due to the Direct Resonance Interaction, as Revealed by Excitation Duration and Intensity Effects on the Decay Behavior
Authors: Taen Shoji , Gondo Yasuhiko
Published: July 2006

The decay of the temperature-independent delayed fluorescence observed in the mixed crystals of phenanthrene in the biphenyl host has been studied at 77 K. That triplet molecules are involved in the mechanism for the emission of temperature-independent delayed fluorescence has been shown by observing the intensities at the instances of the short-pulse excitations effected with different dark periods after the steady-state excitation. It has been found that both the excitation duration and the excitation light intensity affect the decay behavior of the temperature-independent delayed fluorescence. The decay after short-pulse excitation has been observed to be more rapid than the decay after prolonged excitation with the same intensity. When the excitation light intensity is increased with a fixed duration, the delayed fluorescence is observed to decay more rapidly. It is concluded that the decay behavior of the temperature-independent delayed fluorescence can be accounted for in terms of the direct-resonance-interaction mechanism.
Complete Magnetic Anisotropy Films for Perpendicular Recording Prepared by an Electroless Plating Method
Authors: Osaka Tetsuya , Koiwa Ichiro , Okabe Yutaka , Matsubara Hiroshi , Wada Akihide , Goto Fumio , Shiota Norio
Published: July 2006

A complete magnetic anisotropy film was formed by an electroless plating method for a high-density perpendicular recording medium. The Co alloy plating bath, using ammoniacal malonate–tartrate–succinate mixed complexing agents was studied mainly by varying three main metal ion factors in the bath: i.e., the concentrations of NiSO4, NH4ReO4, and MnSO4. The fine columnar structure of magnetic film in a cross section was confirmed by SEM observation. Three different kinds of eight-inch disks A, B, and C, were prepared under selected conditions with magnetic film thickness of 0.50, 0.25, and 0.20 μm respectively. The recording performance was evaluated with a Winchester ring head with a 0.33 μm gap length under various head-medium spacings. A perpendicular recording mode was confirmed, and the following recording densities were obtained: D50=54 and 58 kFRPI for disk A, and 57 and 63 kFRPI for disk B when using 0.20 and 0.15 μm practical usable spacing respectively, and D50=68 kFRPI for disk C when using the more advanced 0.12 μm spacing. It was suggested that the electroless cobalt alloy plating has a high potential as a process for producing perpendicular recording media.
Spectroscopic Behavior of the Alkali Salts of Noncyclic Polyethers: Evidence for Interaction between the End Groups
Authors: Hiratani Kazuhisa
Published: July 2006

The electronic and fluorescence spectra of the alkali salts of noncyclic polyethers exhibiting selective transport for the lithium ion were investigated. In the electronic spectra hypochromicity in CH2Cl2 dependent on the kind of alkali metal ions was observed, and the magnitude of the hypochromic effect decreased in the following order: Li+>Na+>K+>Rb+>Cs+. Using the polar solvents, EtOH and MeCN, instead of nonpolar CH2Cl2, the hypochromicity is small. Also, in the fluorescence spectra, the quenching phenomenon dependent on the kind of alkali metal ions appeared in the same sequence as the hypochromicity in the electronic spectra. It is suggested that these results, together with our previous results, support a stacking structure between the terminal aromatic rings of the lithium salt in a nonpolar solvent, which has been proposed from the inspection of the CPK model building.
Crystal and Molecular Structures of Fenethazine Hydrochloride and Its Cation Radical-Copper(II) Complex Salt
Authors: Obata Atsuo , Yoshimori Masahiro , Yamada Koh-ichi , Kawazura Hiroshi
Published: July 2006

The crystal structures of fenethazine hydrochloride hydrate (FTZ·HCl) and [FTZ H]2+·[CuCl4]2−(FTZ–Cu) were determined. FTZ·HCl crystallized in the monoclinic space group P21/a with a=8.686(1), b=31.660(2), c=6.140(1) Å, β=100.44(1)°, V=1660.5(3) Å3, and Z=4. FTZ–Cu crystallized in the triclinic space group P\bar1 with a=20.433(5), b=12.721(4), c=7.526(2) Å, α=91.31(3), β=94.56(3), γ=99.69(2)°, V=1920.9(1) Å3, and Z=4. The structures were solved using the heavy-atom method and were refined by the block-diagonal least-squares method. The final R values were determined to be 0.052 for FTZ·HCl and 0.050 for FTZ–Cu. The formation of a cation radical causes the phenothiazine ring of the FTZ molecule to be flattened; the dihedral angle between benzene rings is increased from 140.3° for FTZ·HCl to 174.7 or 167.5° for FTZ–Cu. The 2-aminoethyl chain holds a trans conformation in FTZ–Cu and a near gauche form in FTZ·HCl. In FTZ·HCl crystals, the FTZ molecules form a layer along a in which the molecules array the phenothiazine ring as faced with the ring in the neighboring layer. In FTZ–Cu, two FTZ molecules form a pair with a close overlap of the phenothiazine rings, directed approximately perpendicular to a. The CuCl42− is located so as to counterbalance both the positive charge of the ring and the protonated amino group of the side chain.
Calorimetric Determination of Thermodynamic Parameters for the Dissociations of Acids in Dipolar Aprotic Solvents
Authors: Izutsu Kosuke , Nakamura Toshio , Takizawa Katsumi , Takeda Akihiko
Published: July 2006

A calorimetric method has been investigated for the determination of the thermodynamic parameters of acid dissociations in dipolar aprotic solvents. For the dissociations of monoprotonated bases BH+ (B: aniline, pyridine, triethylamine, tributylamine, triethanolamine, 1,3-diphenylguanidine and 1,1,3,3-tetramethylguanidine) in N,N-dimethylformamide, dimethyl sulfoxide (DMSO), acetonitrile and propylene carbonate, the solutions of the bases were titrated with small volumes of a “strong acid,” trifluoromethanesulfonic acid. In each solvent, there was an approximately linear relation of unit slope between ΔH298° and ΔG298° showing that the difference in pKa between different BH+’s can mainly be attributed to the difference in the enthalpy term. As for the solvent effect on pKa, however, the entropy term seems to play an important role. A preliminary study has shown that the calorimetric method is also applicable to the dissociations of HX-type weak acids (benzoic and salicylic acids in DMSO, for example), if the dissociation equilibria are not complicated by such reactions as homoconj ugation.
Synthesis of DMSO–SbCl5(1 : 1) Complex and Its Oxidizing Action toward Alcohols
Authors: Yamamoto Jiro , Ito Satoshi , Tsuboi Takashi , Tsuboi Toshiaki , Tsukihara Kumiko
Published: July 2006

From an equimolar mixture of DMSO and SbCl5 in carbon tetrachloride, a DMSO–SbCl5(1 : 1) complex (1) was formed as a white precipitate in a quantitative yield. The structure of 1 was determined by X-ray crystallographic analysis. Butyraldehydes, para-substituted benzaldehydes and benzils were obtained by the oxidation of butylalcohols, para-substituted benzylalcohols and benzoins using 1 as an oxidizing agent.
Liquid Crystal Materials with Sulfur Atoms Incorporated in the Principal Structure III. Trans and Cis Isomers of New Liquid Crystal Material: 2-(p-Substituted phenyl)-5-alky 1-1,3-dithianes
Authors: Haramoto Yuichiro , Kamogawa Hiroyoshi
Published: July 2006

Trans and cis isomers of 2,5-disubstituted 1,3-dithianes were synthesized by the acid-catalyzed thioacetalization of p-substituted benzaldehydes and dithiols. The results of identifications of trans and cis isomers made by means of 13C-NMR chemical shifts indicate that the isomerism occurred at the 5 position in the 1,3-dithiane ring. Benzaldehydes with electrondonating p-substituents produced less cis isomers than that with the cyano group, which seems to indicate the establishment of an equilibrium in the formation reaction between trans and cis isomers. Several electro-optic properties of trans- and cis-2-(p-cyanophenyl)-5-alkyl-1,3-dithianes were determined by using them as a dopant of mixture of liquid crystals. Mixture added with trans isomers was superior to that added with cis isomers in several points.
Disproportionation of Cyclohexadienes Catalyzed by Metallic Nickel
Authors: Sakai Mutsuji , Kimura Toshiya , Nakaoka Toshiaki , Sakakibara Yasumasa , Uchino Norito
Published: July 2006

Cyclohexadienes, 1,3-cyclohexadiene (1) and 1,4-cyclohexadiene (2), disproportionated to benzene (3) and cyclohexene (4) in the presence of catalytic amounts of metallic nickel prepared from nickel halides and zinc powder in N,N-dimethyformamide (DMF) under nitrogen.
Syntheses of Four Stereoisomers of β-Methyllanthionine
Authors: Wakamiya Tateaki , Oda Yoshiaki , Fukase Koichi , Shiba Tetsuo
Published: July 2006

Four stereoisomers of β-methyllanthionine were synthesized by coupling of N-enzyloxycarbonyl-3-methyl-d-cysteine with β-chloroalanine. 1H NMR analysis and retention time in amino acid analysis were studied on these compounds.
Fluorescence of RbH and RbD Formed by Irradiating the Mixed Gases Rb+Eb and Rb+D2 with Laser Light
Authors: Katô Hajime , Toyosaka Yukiko , Suzuki Tomonari
Published: July 2006

When a mixture of 85Rb, 85Rb2, and D2 was irradiated by laser light at 5145 or 4880 Å, small visible particles appeared and the fluorescence spectra were observed. By analyzing these spectra, we determined the rotational constants Bv and the centrifugal distortion constants Dv and Hv for the X  1Σ+ and A  1Σ+ states of 85RbD. By considering the isotopic dependence of the Dunham coefficients, we determined various molecular constants of 85RbH whose values were in good agreement with the observed fluorescence spectra of 85RbH excited by laser lines at 4762, 4765, and 4880 Å. The process of RbH formation is discussed.
Reaction in the System N(CH3)4–ZrO2–P2O5–H2O. Preparation and Characterization of Framework Zirconium Phosphates (NH4)xH1−xZr2(PO4)3 and HZr2(PO4)3
Authors: Kijima Tsuyoshi , Yajima Yoshiyuki
Published: July 2006

The hydrothermal reaction in the system ZrO2–P2O5–H2O in the presence of tetramethylammonium ions was examined within the temperature range 160–350 °C. This reaction resulted in the formation of framework zirconium phosphates (NH4)xH1−xZr2(PO4)3·yH2O (0.6≤x≤1,y≤0.3) as well as some other phases, including two tetramethylammonium intercalates. The framework phases were rhombohedral with lattice constants of, e.g., a=8.669 and c=24.23 Å for x=1.0. These phases were deammonated at 400–640 °C and converted to the proton-exchanged form HZr2(PO4)3. The protons of this phase are easily exchanged by unhydrated Li+ and Na+ ions, but not by K+ and Cs+, owing to the sieving effect of the bottleneck in the (Zr2P3O12)−1 framework. The acid strength of the proton form is a little weaker than that of α-zirconium phosphate.
Catalysis by Transition Metal Carbides. VI. Hydrogenation of Carbon Monoxide over WC, W2C, and W Powder Catalysts
Authors: Kojima Isao , Miyazaki Eizo , Inoue Yasunobu , Yasumori Iwao
Published: July 2006

WC, W2C, and W were comparatively studied for CO hydrogenation to reveal the catalytic role of carbon alloyed with metals. The main products of the reaction were CH4, CO2, and H2O on these catalysts, but the kinetic data obtained for WC catalyst were different from those for W2C and W catalysts: i.e., the apparent activation energies for CO consumption and for CH4 formation on WC were found to be about three times larger than those on W2C or W. Furthermore, the catalytic activity of WC was about 20 times larger than that of W2C and W. It was suggested that the hydrogenation of CO on WC proceeds via direct hydrogenation of adsorbed CO forming a CHO adsorbed species as an intermediate, whereas on W2C and W catalysts, dissociation of CO occurs in the initial step, followed by further hydrogenation of adsorbed carbon to form CH4. X-ray photoelectron spectroscopic (XPS) studies on WC and W2C showed that the WC surface catalytically activated was almost free from graphite carbon and oxygen as poison, but W2C surface was largely covered with graphite carbon. These distinctive catalytic behavior differences between the carbide catalysts are discussed on the basis of the structure of the active surfaces.
Solvent Effects on Chemical Reactivities II. Aromatic Substitution Reactions
Authors: Ohmae Takayuki
Published: July 2006

The propagator method is applied to the study of solvent effects on reactivities of aromatic substitution reactions. We obtain the following set of results: (1) The influence of nonpolar solvent on electrophilic reactions is opposite to that on nucleophilic reactions; (2) the solvent which has the large dielectric constant weakens the directive power of a substituent group; (3) frontier orbitals control solvent effects on the chemical reactivities of aromatic substitution reactions.
In-Plane Vibrational Modes of Guanine from an ab Initio MO Calculation
Authors: Nishimura Yoshifumi , Tsuboi Masamichi , Kato Shigeki , Morokuma Keiji
Published: July 2006

Harmonic force constants, in-plane vibrational frequencies, and in-plane vibrational modes of guanine have been calculated by an ab initio MO method. The force constants were calculated by the use of an energy gradient method with STO-3G basis set, and then they were corrected into “4-31G force constants” by the scaling factors given by us previously for the case of uracil. The corrected set of force constants could reproduce the observed frequencies of guanine, guanine-7, 9-15N2, guanine-1,3,amino-15N3 (at positions 1, 3 and amino), guanine-8-d (at position 8), guanine-1,9, amino-d4 (at amino and iminos), and guanine-d5. The calculated vibrational modes could also account for the results of earlier experiments on infrared and Raman spectra of guanine residues in 5′-GMP and other nucleotides.
Catalytic Function of Cobalt(III) Complexes with N,N′-Disalicylideneethylenediamine on Oxygenation of t-Butylphenols
Authors: Aimoto Y\={u}ko , Kanda Wakako , Meguro Sadatoshi , Miyahara Y\={u}ji , Okawa Hisashi , Kida Sigeo
Published: July 2006

Catalytic oxygenation of t-butylphenols has been examined with the cobalt(III) complexes with N,N′-disalicylideneethylenediamine (H2salen), K[Co(salen)CO3], Na[Co(salen)(N3)2], K[Co(salen)(CN)2], [Co(salen)(py)2]PF6, and [Co(salen)(NH3)2]PF6. The CO3-complex showed a high catalytic activity while the other complexes a low or no catalytic activity. Based on electronic and ESR spectral investigations, it has been shown that the reaction is initiated by the direct oxidation of t-butylphenols by the CO3-complex through a phenolatocobalt(III) intermediate.
The Crystal Structure of [4R,7S]-7-Isopropyl-4-methyl-2-azepanone [(−)-Menthone Lactam]
Authors: Takayanagi Hiroaki , Hirose Etsuko , Furuhata Kimio , Ogura Haruo
Published: July 2006

The conformation of the title compound was determined by X-ray crystal analysis. The seven-membered lactam ring is in a quasi-chair conformation with the amide chromophore being approximately coplanar.
NMR Spectra of Benzenes Containing Trifluoromethyl Groups
Authors: Takahashi Kensuke , Yoshino Akihiro , Hosokawa Kenzo , Muramatsu Hiroshige
Published: July 2006

The 1H, 13C, and 19F NMR spectra of the nine title compounds were measured. The substituent effect of a trifluoromethyl group were generally additive for the 1H, 13C, and 19F chemical shifts. The assignment of the 13C signals was assisted by the observed coupling constants between the carbon and the fluorine, which were about 275, 35, and 6 Hz for the 1J, 2J, and 3J values of these compounds.
Synthesis of 1-Phenylsulfonylcyclopropanecarboxylic Acid Derivatives
Authors: Takahashi Masahiko , Suzuki Hideo , Kata Yoshimi
Published: July 2006

Ethyl phenylsulfonylacetate was treated with 1,2-dibromoethane in the presence of benzyltriethylammonium chloride and alkali to give 1-phenylsulfonylcyclopropanecarboxylic acid, from which the carbonyl chloride, ester, carboxamide, 1,2-diacylhydrazine, carbonyl azide, carbamate, isocyanate, and γ-butyrolactone derivatives were prepared.
A Practical Synthesis of N-Bromo Imides by Use of Sodium Bromite
Authors: Kajigaeshi Shoji , Nakagawa Takashi , Fujisaki Shizuo , Nishida Akiko
Published: July 2006

N-Bromo imides can be readily prepared under mild conditions by a reaction of imides with sodium bromite in the presence of hydrobromic acid in fairly good yields. The scope and limitation are also presented.
Valence Isomerization between Water-soluble Norbornadiene and Quadricyclane Derivative
Authors: Maruyama Kazuhiro , Tamiaki Hitoshi , Yanai Tetsuya
Published: July 2006

Photoisomerization of 3-(aryicarbamoyl)norbornadiene-2-carboxylic acid 1 to the corresponding quadricyclane derivative 2 in an aqueous alkaline solution was clean and dependent upon the p-substituent of the aryl group. The exothermically reversal reaction of 2 to 1 was also clean but independent upon the substituent.
Hydrogenation of Carbon Monoxide on CO Reducing Catalyst and Solid Acid (III). The Effect of the Pore Size and Acid Properties of Zeolite on the Product Distribution
Authors: Saima Hitoshi , Fujimoto Kaoru , Tominaga Hiro-o
Published: July 2006

Synthesis gas reactions over hybrid catalysts composed of Pd/SiO2 and zeolites and methanol conversion on the same zeolites were studied. The selectivities to aromatic hydrocarbons were about 30% for the methanol conversions over ZSM-5, de-aluminated mordenite, and de-aluminated Y type zeolite (DAY), which possess strong acid sites. When ZSM-5 or mordenites were combined with Pd/SiO2 and subjected to synthesis gas conversion, the selectivities to aromatic hydrocarbons were between 10% and 30%. However, the synthesis gas reaction over the hybrid catalyst composed of Pd/SiO2 and DAY, gave few aromatic hydrocarbons, but aliphatic paraffins with 2 to 6 carbon atoms. Over large pore zeolites like DAY, the diffusion of olefins is so quick that most of the olefins come out of pores to be hydrogenated to paraffins on the Pd/SiO2 catalyst. In contrast, because of the slow diffusion of olefins in the medium size pores of ZSM-5 or mordenite, olefins stay in the pores for long enough to form aromatic hydrocarbons on the strong acid sites before being hydrogenated.
The Conformations of (Z)-2,3,4,7,8,9-Hexahydrooxonin and (Z)-Cyclononene. X-Ray Structure Determinations of Isolaurallene and Neolaurallene, and Force–Field Calculations
Authors: Furusaki Akio , Katsuragi Shin-ichiro , Suehiro Katsunao , Matsumoto Takeshi
Published: July 2006

The molecular structures of isolaurallene and neolaurallene, diastereomeric nonterpenoids (C15H20O2Br2) from the red algae Laurencia, have been determined by X-ray crystallographic analysis. The crystal data are as follows: isolaurallene, orthorhombic, space group P212121, a=10.393(2), b=27.824(4), c=5.397(1) Å, Z=4, Dc=1.669 g cm−3; neolaurallene, monoclinic, space group P21, a=13.338(7), b=4.929(1), c=12.435(5) Å, β=98.22(4)°, Z=2, Dc=1.609 g cm−3. The structures were solved by the heavy-atom method, and refined by the block-diagonal least-squares method; the final R-values were 0.076 and 0.069 respectively. The (Z)-2,3,4,7,8,9-hexahydrooxonin rings in the two substances possess essentially the same conformation. The MM2 force–field calculations have shown that this conformation is almost identical to the most stable one of the 11 minimum-energy conformations found for (Z)-2,3,4,7,8,9-hexahydrooxonin. For comparison, the conformations of (Z)-cyclononene have also been examined by the force–field calculations. Of its 10 minimum-energy conformations obtained, the asymmetric one which Favini et al. already studied has the lowest energy.
The Spectrophotometric Determination of Phosphorus with o-Hydroxyhydroquinonephthalein and Iron(III)
Authors: Fujita Yoshikazu , Mori Itsuo , Kitano Shoko , Kawabe Hiroshi , Koshiyama Yozo
Published: July 2006

On this basis of the coloration formed with o-hydroxyhydroquinonephthalein, an anionic dye, and iron(III) in aqueous media, trace amounts of phosphorus(as orthophosphate ion) was determined. A sample solution containing posphorus and the reagent blank in an amber-colored test tube with a stopper were heated at 40 °C for 20 min in the presence of poly(oxyethylene)sorbitan monolaurate, a nonionic surfactant, as a dispersion agent. Beer’s law was obeyed over the range of ≈1 μg/10 cm3 of phosphorus, and the apparent molar absorptivity of the complex was 2.5×105 dm3 mol−1 cm−1 at 610 nm. The present method was applied to the determination of total phosphorus in water — a sample solution containing small amounts of metal ions —, and the recovery percentage was satisfactory, about 95%. Other compounds containing phosphorus such as 5′-adenosine triphosphate could also be determined without a preliminary treatment.
Chemical Synthesis of Capped Oligoribonucleotides, m7G5′ pppAUG and m7G5′ pppAUGACC
Authors: Sekine Mitsuo , Nishiyama Shin-ichi , Kamimura Takashi , Osaki Yumi , Hata Tsujiaki
Published: July 2006

The fully-protected pAUG (15) and pAUGACC (21) were synthesized by the phosphotriester approach where the phenylthio group was employed as the internal and 5′-terminal phosphate-protecting groups. The partially unblocked oligomers (32) and (33), obtained by alkaline treatment of (15) and (21), were condensed with a capping reagent (1a) in the presence of imidazole by activation with silver nitrate to afford the capped trimer and hexamer protected with the acid-labile protecting groups, i.e., 4,4,′4″-trimethoxytrityl (TMTr), 4-monomethoxytrityl (MMTr), tetrahydropyran-2-yl (THP), and methoxymethylene (mM) groups. The protected capped oligomers were unblocked by a dilute HCl solution to afford m7G5′ pppAUG and m7G5′ pppAUGACC, which were purified by HPLC and characterized by enzyme assays.
Proton Transfer in the Excited State of 1- and 2-Methyl-4-amino-5H-[1]benzopyrano[3,4-c]pyridin-5-one Dimers and Complexes
Authors: Fujimoto Akira , Nakamura Junko , Yamazaki Iwao , Murao Toshiro , Inuzuka Kozo
Published: July 2006

The fluorescence rise and decay times and UV absorption spectra of 1-methyl-4-amino-5H-[1]benzopyrano-[3,4-c]pyridin-5-one (1-MBPP), 2-methyl-4-amino-5H-[1]benzopyrano[3,4-c]pyridin-5-one (2-MBPP), and the 1-MBPP/acetic acid and 2-MBPP/acetic acid systems have been measured in hydrocarbon and hydroxylic solvents at room temperature and 77 K. From these data, a rapid formation of proton-transferred species (tautomers) was found to occur in an excited state for 1-MBPP (or 2-MBPP) hydrogen-bonded dimers in hydrocarbon at 77 K, and for 1-MBPP (or 2-MBPP) hydrogen-bonded complexes with acetic acid in hydrocarbon at room temperature and 77 K. The rise times of the tautomer fluorescence for the dimers and complexes were less than 65 ps. The observed fluorescence lifetimes of the 1-MBPP and 2-MBPP monomers agreed well with the lifetimes calculated using the integrated absorption intensity and fluorescence quantum yield.
Ultraviolet Photoelectron Spectroscopy of Some Fundamental Vinyl Polymers and the Evolution of Their Electronic Structures
Authors: Xian Shang , Seki Kazuhiko , Inokuchi Hiroo , Hashimoto Shimpei , Ueno Nobuo , Sugita Kazuyuki
Published: July 2006

UV photoelectron spectra were measured for polypropylene (PP), poly(vinyl fluoride) (PVF), 1,2-polybutadiene (1,2-PBD), poly(vinyl chloride) (PVC), and poly(vinyl alcohol) (PVA). Their threshold ionization energies were found to be 8.5, 9.2, 7.5, 8.8, and 8.0 eV (1 eV≅0.1602 aJ), respectively. The evolution of their electronic structures (from those of small related molecules) were analyzed, mainly, by using the photoelectron spectra of these small compounds (including the new data of 1,2-propanediol). The data of previously measured polyethylene (PE) and polystyrene (PS) were analyzed together. With the results, the polymers were classified into three groups according to the increasing order of localization of the positive hole in the cationic state: (1) PE, PP, and PVF, (2) 1,2-PBD, PVC, and PVA, and (3) PS as a representative of aromatic-pendant polymers.
Spirolactone of Xanthene. II. Synthesis and Molecular Structure of 2′,5,7′-Trichlorospiro[benzofuran-3(2H),9′-[9H]xanthen]-2-one
Authors: Kimura Michio
Published: July 2006

The title compound has been synthesized by the novel condensation reaction of p-chlorophenol with oxalic and sulfuric acids; its crystal and molecular structures have been determined by the single crystal X-ray diffraction method. The space group is C2/c. There are eight molecules of the title compound in the unit cell of dimensions a=21.316(9), b=17.267(4), c=9.158(6) Å, and β=94.05(5)°. The structure was solved by the direct method and refined by the block-diagonal least-squares method to a value of 0.088 for R using 1993 independent observed reflections with Fo>3σ(Fo). The molecule possesses three phenyl rings fused to spirolactone and the dihedral angles between the phenyl rings are 73.60°, 83.60°, and 22.81°.
The Preparation and Spectral Properties of trans(CN)-[Co(CN)2(tmdda)]− and -[Co(CN)2(l-ala)2]− Complexes
Authors: Kanamori Kan , Nunomura Yoko , Takashima Masumi , Nagata Kiyonori , Kawai Kiyoyasu , Hidaka Jinsai
Published: July 2006

All-trans- and trans(CN),cis(N)-[Co(CN)2(l-ala)2]− and trans(CN)-[Co(CN)2(tmdda)]− were newly prepared; here, tmdda denotes trimethylenediamine-N,N′-diacetate. These complexes were characterized from their electronic absorption, NMR, and Raman spectra. The CD spectra of two trans(CN) isomers of the bis(l-alaninato) complex are also presented.
Reduction of Nitrobenzenes on Thin Aluminium Oxide Utilized in Inelastic Electron Tunneling Spectroscopy
Authors: Monjushiro Hideaki , Murata Katsuo , Ikeda Shigero
Published: July 2006

Chemical interactions between aromatic nitro compounds and thin aluminium oxide grown on aluminium film were studied by the combined use of inelastic electron tunneling spectroscopy (IETS) and X-ray photoelectron spectroscopy (XPS). IET spectra of nitrobenzoic acids and nitrophenols show that nitro groups of these compounds are reduced on the oxide and result in the corresponding amino compounds. In this conversion reaction, oxygen atoms of nitro group are consumed for the growth of the oxide layer and hydrogen atoms of the surface hydroxyl groups are used for the amidation reaction. The intermediate of the reaction is identified to the corresponding nitroso compounds from the XPS analysis.
The Reaction of [CoL2] (L=5-Chloro- or 5-Nitro-8-quinolinolate Ion) with Nitrogen Monoxide
Authors: Miki Eiichi , Ishimaru Kazuomi , Mizumachi Kunihiko , Ishimori Tatsujiro , Tanaka Mikio
Published: July 2006

[CoL2]·nH2O (L=5-chloro-8-quinolinolate ion, n=4; L=5-nitro-8-quinolinolate ion, n=5) reacted with nitrogen monoxide in CH2Cl2 at ca. 253 K to give [CoL2(NO)] with NO− group. [CoL2(NO)] reacted further with nitrogen monoxide in 10 v% pyridine–DMF at room temperature to give [CoL2(NO3)(py)]·nDMF·0.5py (L=5-chloro-8-quinolinolate ion, n=0; L=5-nitro-8-quinolinolate ion, n=1) with liberation of dinitrogen oxide. [CoL2]·nH2O also reacted with nitrogen monoxide in the pyridine–DMF to give the same nitrato complexes. In pyridine, [CoL2]·nH2O gave [CoL2(NO3)(py)]. In DMF, [CoL2]·nH2O reacted with nitrogen monoxide at room temperature to give [CoL2(NO)]·0.5H2O (L=5-chloro-8-quinolinolate ion) or [CoL2(NO2)(DMF)]·2H2O (L=5-nitro-8-quinolinolate ion).