bluuebunny/crossref_metadata_2025 huggingface dataset:
The Effect of Ultraviolet Radiation on the Wattability of Silicone Polymers
Authors: Esumi Kunio , Meguro Kenjiro , Schwartz Anthony M , Zettlemoyer Albert C
Published: July 2006

The effect of UV radiation in air on the wettability of silicone polymers was studied by measuring the contact angles. From the contact-angle data, the surface energies were also calculated. As the irradiation progressed, the surface energy of the polar component increased, while the surface energy of the dispersive component remained constant, for all the samples. This increase in surface energy is attributable to a surface photooxidation of the silicone polymers. Especially, poly(diphenylsiloxane) showed a remarkable increase in the surface energy of the polar component after the irradiation.
Preparation and Properties of Octahedral Nickel(II) Complexes with and Schiff Bases Derived from Substituted Salicylaldehydes and Bis(2-aminoethyl) Sulfide
Authors: Hori Kiichi , Takahashi Kazuko
Published: July 2006

The octahedral complexes listed in the title have been prepared. The magnetic and spectral properties of these complexes indicate that the non- and 5-substituted complexes have a structure bridged by the phenolic oxygen of the Schiff bases and the 3-substituted complexes probably are mononuclear.
An Ultrasonic Nebulizer for Microliter Samples in Inductively Coupled Plasma Emission Spectrometry
Authors: Kawaguchi Hiroshi , Tanaka Tomokazu , Mizuike Atsushi
Published: July 2006

A batch type ultrasonic nebulizer is constructed for 300-μl samples to produce an aerosol for more than 60 s. Desolvation facilities are not used. The internal standard method is employed to compensate for the instability of nebulization.
Oxidizing Action of Complex of N,N-Dimethylbenzylamine Oxide with SbCl5
Authors: Yamamoto Jiro , Tanioka Yukio , Umezu Masahiro
Published: July 2006

A 1:1 complex of N,N-dimethylbenzylamine oxide–SbCl5 (1) was prepared in carbon tetrachloride quantitatively. Complex 1 was found to be a better reagent for oxidation of benzoin, furoin, benzyl alchols and pinacols than the complexes pyridine N-oxide–SbCl5 and trimethylamine oxide–SbCl5. The reaction path in oxidation of benzhydrol with 1 is described.
Solvent Effect on Photooxidation of Triphenylphosphine Selenide Sensitized by Polymer-supported Rose Bengal
Authors: Tamagaki Seizo , Akatsuka Ryuji
Published: July 2006

Solvent effect on the photooxygenation of triphenylphosphine selenide was examined by using cross-linked polystyrene- or silica gel-anchored Rose Bengal as sensitizers. Different types of solvent dependency of the product yields were observed in each case.
Friedel-Crafts Reactions of Benzene with 1-Phenylpropanols. Effects of CuCl2, Cu2Cl2, and Decalin
Authors: Ichikawa Katsuhiko , Chano Keizo , Inoue Masashi , Sugita Toshio
Published: July 2006

Highly regioselective formation of 1,1-diphenylpropane was observed when copper(I) or (II) chlorides was added to the aluminium chloride-catalyzed reaction of benzene with 1-phenyl-1-propanol. In the reaction with 1-phenyl-2-propanol, the addition of copper salts increased the formation of 1,1-diphenylpropane. The addition of decalin diminished the alkylation reaction to give a reduction product.
X-Ray Crystallographic Analysis of 3α,5-Epoxy-6β-3β-methyl-A-homo-4-oxa-5α-cholestane, a Major Product of Photo- and Thermally-induced Radical Rearrangements of Hypoiodites of 3α-and 3β-methyl-5-cholesten-3-ols
Authors: Furusaki Akio , Katayama Chuji , Suginome Hiroshi
Published: July 2006

The major product of photo- and thermally-induced radical rearrangements of hypoiodites of 3α-and 3β-methyl-5-cholesten-3-ols in the presence of iodine with mercury(II) or silver(II) oxide has been established as 3α,5-epoxy-6β-iodo-3β-methyl-A-homo-4-oxa-5α-cholestane by means of X-ray crystal structure analysis.
A One Step Transformation of the Sodium Salt of α-aci-Nitrotoluene into 3,4,5-Triphenylisoxazole
Authors: Fukunaga Kimitoshi , Okamoto Akihiko , Furumoto Keiji , Kimura Makoto
Published: July 2006

3,4,5-Triphenylisoxazole was produced by the reaction of the sodium salt of α-aci-nitrotoluene with the 1-cyano-1-methylethyl radical. The reaction was found to proceed via one electron transfer from α-aci-nitrotoluene anion to a 1-cyano-1-methylethyl radical.
Interaction between Hydrophilic Proteins and Nonionic Detergents Studied by Surface Tension Measurements
Authors: Nishikido Nagamune , Takahara Tomoyuki , Kobayashi Hideki , Tanaka Mitsuru
Published: July 2006

The surface tensions of the systems of hexa(oxyethylene) dodecyl ether (C12E6) vs. lysozyme (Lyz) or bovine serum albumin (BSA) were measured for constructing the binding isotherms, since the surface tension method is more convenient for the systems of nonionic detergents and proteins than is equilibrium dialysis. The obtained binding isotherms depend on the protein concentration; this effect is much more remarkable for Lyz–C12E6 systems than for BSA–C12E6 ones. The binding isotherms of BSA–C12E6 systems obey the Scatchard equation, and the maximum number and estimated free energy for C12E6 binding to BSA are comparable to those for the system of Triton X-100 and BSA determined by equilibrium dialysis. The agreement suggests that the surface tension method is sound and has advantages over equilibrium dialysis for the estimation of the number of detergent molecules bound to protein. In the systems of Lyz–C12E6, the binding isotherms follow the Freundlich-type equation rather than the Scatchard equation. The remarkable protein concentration dependence of the binding isotherms and this result suggest the occurrence of protein aggregation.
Further Comments on the Line-broadening of the Chlorine 35 NMR Spectra and the Local Structure around a Chloride Ion in Aqueous Solutions of Non-electrolytes
Authors: Yudasaka Masako , Sugawara Tadahi , Iwamura Hiizu , Fujiyama Tsunetake
Published: July 2006

The remarkable line-broadenings of the 35Cl NMR spectra observed for the KCl in aqueous solutions of non-electrolytes were explained well by considering the formation of water-cages which surround the non-electrolytes. This result, in turn, suggests that the line-width measurement is a useful method for determining local structures formed in solutions.
The Structure of Dichloro(4-hydroxy-l-proline)cadmium(II)
Authors: Yukawa Yasuhiko , Inomata Yoshie , Takeuchi Toshio , Shimoi Mamoru , Ouchi Akira
Published: July 2006

An X-ray diffraction study of the title complex has been carried out. The crystal is monoclinic, with the space group P21; Z=2; a=8.196(4), b=7.275(3), c=7.740(4) Å, β=103.73(4)° Full-matrix least-squares refinements have led to the final R value of 0.030. The structure consists of one-dimensional polymers bridged by chlorine atoms and a carboxyl group. Four chlorine atoms coordinate to a cadmium atom and form a square plane. The planes extend in the direction of the b axis like an infinite folding screen, sharing opposite edges. From the trough positions in the zigzag structure, the carboxyl oxygen atoms of 4-hydroxy-l-proline coordinate forkedly to two cadmium atoms. The ligand is a zwitter ion in the complex.
Synergistic Effect of Nitrogen Neutral Bases in the Solvent Extraction of Zinc(II) and Cadmium(II) Diphenylcarbazonates
Authors: Yamada Etsu , Nakayama Eiichiro , Kuwamoto Tooru , Fujinaga Taitiro
Published: July 2006

The extraction behavior of zinc and cadmium with diphenylcarbazone(DPC) into benzene and chloroform were studied in both the absence and presence of neutral bases(S). In the case of chloroform, all of the neutral bases gave rise to adduct complexes with the formula of M(DPC)2S. On the other hand, in the case of benzene, the adduct complexes can be represented as M(DPC)2S for all neutral bases except for 1,10-phenanthroline(phen), in which the adduct complexes can be expressed as M(DPC)2(phen)2. The stability of the adduct complexes is related not only to the basicity of the bases, but also to the steric effect attributable to substitution. Furthermore, the adduct-formation constant increase in the following order against the normalized values of basicity: pyridine bases<2,2′-bipyridyl<1,10-phenanthroline derivatives. This order agrees with the increasing order of the coordinated ability as ligands. The basicity of the bases has a larger effect on the adduct-formation constants for Cd than on those for Zn. This may be attributed to the fact that Zn chelates have greater stability than the Cd chelates, as a result, the “residual Lewis acidity” of Zn is smaller than that of Cd, and therefore zinc chelates form less stable adducts.
Synthesis, Characterization, and Crystal Structure of Substituted Derivatives of (Tetraazacyclotetradecatetraenato)copper(II) Complexes
Authors: Matsumoto Naohide , Imaizumi Masahiko , Ohyoshi Akira
Published: July 2006

(Tetraazacyclotetradecatetraenato)copper(II) complexes with the general formula [Cu(Me2E2[14]tetraenatoN4)], where E denotes the substituent group of acetyl, propionyl, isobutyryl, benzoyl, p-methylbenzoyl, or p-nitrobenzoyl, have been prepared via electrophilic substitution of the parent complex [cu(Me2[14]tetraenatoN4)] with acid chlorides, and characterized by elemental analyses and infrared spectra. For the p-substituted benzoyl derivatives, both the position of d-d electronic band maxima and reduction potential assignable to Cu2+e→Cu+ vary linearly with the Hammett substituent constants. The crystal structure of one of the complexes [Cu(Me2Acyl2[14]tetraenato)4]·H2O has been determined by the single-crystal X-ray diffraction method. The copper atom assumes a square planar coordination geometry and the overall conformation of the complex assumes a chair-like shape, where the seat and the rests are formed by the coordination plane (CuN4) and the two conjugated six-membered chelate rings respectively.
Polarographic Behavior of Cobalt-1-Nitroso-2-naphthol Complex in Ammonium Citrate and Tartrate Solutions
Authors: Sugawara Masao , Uchida Toyoaki , Kambara Tomihito
Published: July 2006

The reduction behavior of cobalt(II) in ammonium citrate and tartrate solutions containing 1-nitroso-2-naphthol was investigated by means of d.c, a.c, normal and differential pulse polarography (n. p. p. and d. p. p.). When cobalt(II) is added to the supporting electrolyte of citrate or tartrate in the presence of the nitrosonaphthol, the reduction potential of 1-nitroso-2-naphthol shifts to a more negative value, the well-defined a. c. and d. p. p. peaks appearing. The drop time-potential curve indicated that adsorption of nitrosonaphthol as well as its reduction product at the mercury surface occurs. The analytical potentiality of the use of nitrosonaphthol for the microdetermination of cobalt(II) is also described.
Aldol Condensations Catalyzed by Co(II) Complexes of Pyridine-containing Copolymers
Authors: Watanabe Ken-ichi , Imazawa Atsushi
Published: July 2006

The cross aldol condensations of aldehydes and ketones catalyzed by Co(II) complexes of pyridine-containing copolymers proceed under neutral conditions in DMF or DMSO to afford α,β-unsaturated ketones without any byproduct. The solid complex catalysts are capable of repeated use. The reactions of aromatic aldehydes and ketones give good results but not those of aliphatic compounds. Effects of substituent groups in chalcone formation are observed. The catalytic reaction features with the polymer-complex catalysts are compared with that with Co(II)–pyridine complex. The polymer-complex-catalyzed aldol condensations are discussed briefly in relation to the enzymatic reaction of Class II aldolase (metalloenzyme).
Zero-field Splitting Tensor and Orientation of the Phosphorescent-state Benzo[h]quinoline in Biphenyl Host
Authors: Sekiya Hiroshi , Gondo Yasuhiko
Published: July 2006

ESR absorption has been observed in a single-crystal solid solution of benzo[h]quinoline in biphenyl under UV irradiation at 120 K. The triplet-state zerofield splitting tensor and the guest orientation are reported, in comparison with the previous results on benzo[f]quinoline.
Reactivities of Stable Rotamers. XI. Rotamer Distributions and Some Addition Reactions to the Carbonyl in 9-[2-(Substituted carbonyl)-1-naphthyl]fluorene Rotamers
Authors: Saito Ryo , Oki Michinori
Published: July 2006

Rotational isomers (sp and ap) of several 9-[2-(substituted carbonyl)-1-naphthyl]fluorenes where the substituent is methyl, phenyl, hydroxyl, methoxyl, 1-imidazolyl, or others have been obtained as stable entities. Barriers to rotation in these compounds were ca. 26.5 kcal for the process sp→ap but those for the reverse (ap→sp) were dependent on the substituent, ranging from 23.8 to 25.3 kcal/mol at 55 °C. The difference is reflected in the populations of rotamers: if the substituent is a hydroxyl, the sp/ap value becomes as large as ca. 20. The relative instability of the ap form was attributed to twisting of the carbonyl plane from that of naphthalene. Infrared spectra support the twisting. Addition reactions to the carbonyl occur smoothly in the sp conformation but they do not occur to a detectable extent in the ap conformation, if the substituent on the carbonyl is larger than hydrogen. The results are attributed to the steric effect of the fluorene ring.
The Ammonolysis of Trichloroethylene to Glycine
Authors: Inoue Masami , Enomoto Saburo
Published: July 2006

Glycine was obtained by the ammonolysis of trichloroethylene with aqueous ammonia. Various alkalines, such as alkaline metal hydroxides, carbonates, and hydrogencarbonates, accelerated the reaction; the yield of glycine was 40–70% after a 4 h reaction at 180 °C. Our results on the effect of alkalines indicate that ammonolysis proceeded sequentially via the formation of aminoacetonitrile. A good yield of the intermediate compound, aminoacetonitrile, was obtained by heating trichloroethylene at 70 °C with anhydrous ammonia under reaction conditions.
The Reactions of Singlet NH Radicals with Methyl and Ethyl Alcohols in the Liquid Phase
Authors: Kawai Jun , Tsunashima Shigeru , Sato Shin
Published: July 2006

The reactions of the singlet NH(a1Δ) radicals with alcohols were studied by the photolyses of hydrogen azide in liquid methyl and ethyl alcohols at the temperature of Dry Ice–methyl alcohol and at 0 °C. The main products were nitrogen, ammonia, and oxime ethers; acetaldehyde oxime O-ethyl ether from ethyl alcohol and formaldehyde oxime O-methyl ether from methyl alcohol. The relative yields of the products were independent of the changes in the reaction temperature and in the concentration of the hydrogen azide examined. Methoxyamine or ethoxyamine, a possible insertion product of the singlet NH into the O–H bond of alcohol, was detected as a form of oxime ether by the reactions with the aldehyde eventually formed. It was concluded that the singlet NH radicals can effectively insert into the O–H bond of the alcohol.
Reactions of 3-Acetyltropolone and Its Methyl Ethers with o-Aminophenol
Authors: Imafuku Kimiaki , Shigenobu Akihiro , Ogura Makoto
Published: July 2006

3-Acetyltropolone (1) and 2-acetyl-7-methoxytropone (2a) reacted with o-aminophenol in ethanol to afford 2-acetyl-7-(o-hydroxyanilino)tropone (3). The reaction of 3-acetyl-2-methoxytropone (2b) gave 3-acetyl-2-(o-hydroxyanilino)tropone (5). The compounds 3 and 5 were cyclized to 6-acetyl- and 10-acetylcyclohepta[b][1,4]benzoxazines (4 and 6), respectively, by heating their acetic acid solutions in the presence of a trace amount of concentrated sulfuric acid. The compounds 4 and 6 were also obtained directly from 1 (or 2a) and 2b, respectively, by the reaction with o-aminophenol in acetic acid. The compound 5 exists as a tautomeric mixture with 5′.
Photosensitized Desulfurization of Heterocyclic Thioketones and Its Accompanied Chemiluminescence
Authors: Suzuki Nobutaka , Sano Kaniti , Wakatsuki Satoshi , Tani Noriyuki , Izawa Yasuji
Published: July 2006

Photosensitized oxygenation of 10-methyl-9(10H)-acridinethione, 9H-xanthene-9-thione, and 9H-thioxanthene-9-thione at −78 °C gave the corresponding ketones, 10-methyl-9(10H)-acridinone, 9H-xanthen-9-one, and 9H-thioxanthen-9-one quantitatively in a 3–10 min-irradiation. Weak chemiluminescence was observed from the irradiated solution upon warming-up.
The Investigation of Energy Efficiency of the ZnO Semiconductor Photoelectrode by Photothermal Measurement
Authors: Maeda Yasuhisa , Fujishima Akira , Honda Kenichi
Published: July 2006

The energy efficiency of a polycrystalline ZnO photoanode in an electrolyte solution containing redox agents was investigated by measuring the temperature change of the electrode surface. The results of photothermal measurements show that the energy efficiency depends on the kind of redox agents used. Reducing agents with more positive potentials gave larger energy efficiencies, but the potential must be negative enough to decrease ZnO dissolution.
Kinetic Studies of the Micelle System of Octylammonium Alkanoates in Hexane Solution by the Ultrasonic Absorption Method
Authors: Yamashita Teruyo , Yano Hiroshige , Harada Shoji , Yasunaga Tatsuya
Published: July 2006

Ultrasonic absorption was measured in hexane solutions of octylammonium alkanoates (nonanoate, decanoate, dodecanoate, and tetradecanoate). The value of critical micelle concentration (CMC) was determined to be 0.02 M (1 M=1 mol dm−3) for all the surfactants. The excess ultrasonic absorption, observed in the solutions above the CMC, was ascribed to the association-dissociation of the monomer to and from the micelle. From the concentration dependences of the ultrasonic parameters, the mean aggregation number of the micelle, the rate constants, and the enthalpy change of the above reaction were obtained. These results were discussed in relation to the shape of the reversed micelle and the solute-solvent interactions.
The Complex Formation of Poly(N-vinylpyrrolidone) with Manganese Dodecyl Sulfate in Water Studied by ESR
Authors: Aizawa Masayuki , Komatsu Tsuyoshi , Nakagawa Tsurutaro
Published: July 2006

ESR measurements of Mn2+ ions in aqueous manganese dodecyl sulfate (Mn(DS)2) solutions with or without 0.05% poly(N-vinylpyrrolidone)(PVP) were carried out at 30 °C. The dependences of linewidths and of absorption intensities on the Mn(DS)2 concentration in (Mn(DS)2+0.05% PVP) solutions changed abruptly at a concentration where a PVP–Mn(DS)2 complex begins to form. The same dependence in Mn(DS)2 solutions was found around the CMC of Mn(DS)2 in water. From the quantitative analysis of the data obtained, it was concluded that the Mn(DS)2 molecules in the complex form a nearly micelle-like aggregate, and that most of Mn2+ ions bound onto the micelle-like aggregate or the Mn(DS)2 micelle exist in the Stern layer. In addition, the PVP concentration dependence of the similar quantities in (Mn(DS)2+PVP) solutions with a constant Mn(DS)2 concentration suggested that the polymer-surfactant complex changes its structure at higher PVP concentrations.
Preparation and Electrochemical Behaviors of Phenoxide-coordinated Iron(III) Porphyrins
Authors: Sugimoto Hiroshi , Ueda Nobuhiro , Mori Masayasu
Published: July 2006

A new series of iron(III) porphyrins having various phenoxide anions as the axial ligand, [FeIII(porphyrin)(4-X–C6H4O−)] (porphyrin=octaethylporphyrin and tetraphenylporphyrin; X=OCH3, CH3, H, C6H5, Cl, Br, COCH3, CN, CHO, and NO2) were synthesized. All these complexes are five-coordinated high-spin complexes (S=5⁄2). Their electrochemical behaviors were investigated by the cyclic voltammetry and the controlled potential coulometry. The complexes showed significantly negative potentials for the FeII/FeIII redox couple (−0.4–−0.8 V). A good linear relationship was found between the half-wave potentials of the FeII/FeIII redox couple and the Hammett σ-values of the substituent X. A new characteristic feature is the appearance of the redox peaks of the coordinated phenoxide anions near the redox couple of the porphyrin ring oxidoreduction. The role of the tyrosine-67 in the enzymatic mechanism for cytochrome c is discussed.
Reduction of Aromatic Compounds by Solvated Electrons Generated at Cathode
Authors: Misra Ram A , Yadav Ashok K
Published: July 2006

Phenol, anisole, and toluene can be reduced electrochemically to cyclohexanol, methoxycyclohexane, and methylcyclohexane respectively, in ethanol containing hexamethylphosphoric triamide (HMPA) at aluminium cathode. The reduction of these aromatics is believed to occur due to electrochemically generated solvated electrons.
Additive Effect of CF3Cl on an Oxidation Reaction in Shock Waves. I. Study with H2–O2
Authors: Hidaka Yoshiaki , Kawano Hiroyuki , Suga Masao
Published: July 2006

Sample gases, H2–O2, H2–O2–CF3Cl, and CF3Cl, highly diluted with Ar were heated behind reflected shock waves over the temperature range 1400–2200 K and an additive effect of CF3Cl at various concentrations (0–0.5%) was studied by monitoring ultraviolet and visible emissions. At a temperature below 2200 K, C2* and CH* species were found to be formed in the oxidation reaction of H2 together with CF3Cl, but hardly formed in the thermal decomposition of CF3Cl. The addition of small and large amounts of CF3Cl increased and decreased, respectively, the intensity of OH* emission from the H2–O2 mixture heated to a constant temperature. An ignition delay time at a fixed temperature above 1400 K was found to shorten with an increase in the concentration of CF3Cl. A brief discussion is given of the mechanism for the formation of the chemiluminescent species.
The Dechlorination of Polychlorinated Biphenyls by UV-irradiation. VIII. Reactions of 2,3- and 3,4-Dichlorobiphenyl in a 2-Propanol Solution
Authors: Nishiwaki Tohru , Shinoda Tsutomu , Anda Kinji , Hida Mitsuhiko
Published: July 2006

The photodechlorinations of 2,3-dichlorobiphenyl (2,3-DCB) and 3,4-dichlorobiphenyl (3,4-DCB) in 2-propanol gave 3-chlorobiphenyl and 4-chlorobiphenyl respectively. The quantum yields of monochlorobiphenyl formation were 0.2 for 2,3-DCB and 0.06 for 3,4-DCB, independent of the substrate concentration and the wavelength of the exciting light. On the basis of the results obtained in quenching experiments using cis-1,3-pentadiene, it was concluded that 2,3-DCB was photodechlorinated exclusively in the excited singlet state, while 3,4-DCB was photodechlorinated in both excited singlet and triplet states. In the case of 3,4-DCB, the relative contributions of excited singlet and triplet states to the total dechlorination were evaluated as 0.8 and 0.2 respectively. The participation of the excited triplet state in the photodechlorination of 3,4-DCB was ascertained both by quenching reactions with biacetyl as a quencher and by photosensitized dechlorinations with acetone and acetophenone as sensitizers.
Infrared Spectra and Conformation of N-Acetylthiourea
Authors: Aruna Srinivasan , Shanmugam Guruswamy , Manogaran Sadasivam , Sathyanarayana D N
Published: July 2006

Infrared spectra of N-acetylthiourea (ATU) and its N,N,N′-trideuterated compound have been examined in the range 4000–50 cm−1. A complete vibrational assignment with a normal coordinate treatment based on a Urey-Bradley type intramolecular potential function supplemented with valence force function for the out of plane and torsional modes is proposed and the feature of the thioureido vibrations explained. A molecular orbital study by the CNDO/2 method of ATU and its oxygen analog is undertaken and the results are analyzed for a comparative study of the molecular electronic structure and conformation.
Reference Materials for the Pyrolysis Gas-chromatographic Determination of Ammonia, Nitrogen, Nitrogen Monoxide, Carbon Monoxide, and Carbon Dioxide
Authors: Miyokawa Kikuo , Abe Naoki , Masuda Isao
Published: July 2006

Four compounds are proposed as the reference materials to calibrate the pyrolysis gas chromatograph in the determination of inorganic gases: [Co(NH3)5Cl]Cl2 for NH3, [Co(NH3)5NO2]Cl2 for N2, [Co(NH3)5NO]Cl2 for NO, and PbC2O4 for both O and CO2. On pyrolyses, the gas evolution of these compounds were stoichiometric, and the peak area corresponded fairly well to the weight of the compound. Under the condition employed, 7.3–138 μmol of NH3, 2.2–67 μmol of N2, 2.0–61 μmol of NO, 0.84–26 μmol of CO, and 2.5–76 μmol of CO2 were analyzed by using 0.5–15 mg of the compounds.
Photolysis of o-(N-Alkylacylamino)benzophenones
Authors: Hasegawa Tadashi , Kosaku Satomi , Ueno Junko , Oguchi Sh\={o}shichi
Published: July 2006

The photochemical reactions of o-(N-alkylacylamino)benzophenones have been studied. Photochemical behavior of the (acylamino)benzophenones was dependent on the solvent polarity. The (acylamino)benzophenones underwent photodeacylation in polar solvents and photodealkylation in nonpolar solvents.
An Effective Process for Treatment of Malodor in Exhaust Gas by Hypochlorite
Authors: Abe Kenzo , Machida Wataru
Published: July 2006

Pilot-plant studies were carried out to find out the optimum conditions for hypochlorite-oxidation treatment of malodorous multi-components in exhaust gas from night soil treatment plants. A two-step process was proved to be the most effective: a part of malodorous components are absorbed and oxidized in the first packed-tower into which a pH 7 aqueous solution of sodium hypochlorite slowly introduced and then unreacted components are oxidized in the second tower with a pH 11 solution.
The Wet Oxidation of Organic Compounds Catalyzed by Co–Bi Complex Oxide
Authors: Imamura Sei-ichiro , Kinunaka Hiroshi , Kawabata Nariyoshi
Published: July 2006

The wet oxidation of various organic compounds was carried out in the presence of the Co–Bi (5:1) complex oxide catalyst. The catalyst was especially effective for the oxidation of all refractory lower carboxylic acids, which are intermediates in the wet oxidation of many organic compounds.
Thermal Decomposition of Calcium Sulfate Dihydrate under Self-generated Atmosphere
Authors: Isa Kimio , Okuno Hiroki
Published: July 2006

Dehydration of calcium sulfate dihydrate was studied by means of simultaneous TG-DTG-DTA under various sealed atmospheres corresponding to three systems open, completely sealed, and quasi-sealed. Two dehydration steps could be detected under self-generated atmospheres by using 12.3, 18.7, 30.0, and 250 μm tungsten wires. This new method enables us to identify intermediates more easily than any other techniques hitherto adopted. Endothermic DTA peaks appeared earlier, at 129 and 133 °C, than the point of decreasing TG. This technique, resembling the quasi-isothermal and -isobaric thermogravimetry (Q-TG), is superior to Q-TG in that it requires smaller amounts of sample.
Preparation and Structure of μ-Oxalato-bis{μ-oxo-μ-sulfido-bis[(oxalato)oxomolybdate(V)]} Complex, K6[{Mo2O3S(ox)2}2(ox)]·10H2O
Authors: Shibahara Takashi , Ooi Shun’ichiro , Kuroya Hisao
Published: July 2006

The μ-oxo-μ-sulfido-(oxalato)molybdate(V) complex has been prepared and characterized by X-ray analysis. The potassium salt crystallizes in monoclinic system, space group C2/c, with cell dimensions a=13.640(3), b=20.296(3), c=15.213(4) Å, β=106.42(2)°, and Z=4. The structure was solved by the heavy-atom technique and refined by the block-diagonal least-squares method to R=0.048 for 3552 independent reflections. The complex anion is tetrameric, two dimeric Mo2O3S(ox)2 moieties being bridged by one oxalato ligand. Both the molybdenum atoms in the dimer are bridged by one sulfur and one oxygen atoms. Each molybdenum atom has distorted octahedral environment; two oxygen atoms of a bidentate oxalato ligand, bridging sulfur and oxygen atoms in the equatorial plane, a terminal oxygen and one of the bridging quadridentate oxalato ligand oxygens. The complex can be denoted as K6[{Mo2O3S(ox)2}2(ox)]·10H2O and has an approximate C2h symmetry, with a crystallographic center of symmetry. The Mo–O (quadridentate bridging oxalato) bonds (2.304(4), 2.302(4) Å) are evidently longer than the Mo–O (bidentate oxalato) bonds (2.112(4), 2.102(4), 2.093(4), 2.120(4) Å). The influence of the bridging oxalato ligand on the geometry of Mo2O3S core will be discussed.
Thermal Cis-to-Trans Isomerization of [CoX2en2]X (X=Cl, Br)
Authors: Tsuchiya Ryokichi , Uehara Akira , Muramatsu Yoshinori
Published: July 2006

By measuring calorimetrically the heats of reaction of solid cis- and trans-[CoX2en2]X (X=Cl, Br) with alkaline sodium sulfide solution, the heats of isomerization were obtained as −11.4 kJ mol−1 for cis-[CoCl2en2]Cl(s)=trans-[CoCl2en2]Cl(s) and −6.4 kJ mol−1 for cis-[CoBr2en2]Br(s)=trans-[CoBr2en2]Br(s). Assuming the entropy changes from cis- to trans-form, ΔS, to be −0.0116 kJ mol−1 K−1 at 25 °C statistically, the free energy changes were calculated as ΔG°=8.0 kj mol−1 and −3.0 kJ mol−1 for the isomerization of cis-[CoCl2en2]Cl and cis-[CoBr2en2]Br respectively. From these thermodynamic data, cis-to-trans isomerization was expected to occur in [CoX2en2]X (X=Cl or Br), which was verified experimentally by thin-layer chromatography and the spectral measurement.
Kinetic Studies of Solvent Extraction of Metal Complexes. VIII. Rate of Complex Formation and Solvent Extraction of Iron(III) in Aqueous Perchlorate Solutions with 1,1,1-Trifluoro-2,4-pentanedione
Authors: Sekine Tatsuya , Inaba Kazuho
Published: July 2006

The rate of the extraction of iron(III) in aqueous 4 mol dm−3 sodium perchlorate solutions with 1,1,1-trifluoro-2,4-pentanedione (Htfa) into carbon tetrachloride was measured, and the rate constants for the controlling reactions in the aqueous phase:

Fe3++Htfa→Fe(tfa)2++H+and Fe(OH)2++Htfa→Fe(tfa)2++H2O,

were calculated. These constants were also determined from spectrophotometric measurements of the aqueous solutions in the absence of the organic phase. The two series of rate constants obtained by the independent experiments agreed well. It was pointed out that equilibrium constants among the complexes in the aqueous and organic phases are indispensable in order to make a precise discussion of the solvent extraction of metal ions when aqueous-complex formation controls the whole process.
Chemical Effects Due to the (γ, n) Reaction and Isomeric Transition Studied by a Vacuum Sublimation Technique
Authors: Sekine Tsutomu , Sakanoue Masanobu , Nakamura Takashi , Yoshihara Kenji
Published: July 2006

Chemical effects of the 59Co(γ,n)58m,gCo reaction and of the isomeric transition of 58mCo in Co(acac)3, Co(acac)2, and Co(acac)2·2H2O were studied by using a vacuum sublimation technique. In the isomeric transition, highly enriched 58gCo(acac)2 was separated from 58mCo(acac)3. By the (γ,n) reaction, about a half of the radioactive nuclides produced were found in the form of Co(acac)2 after irradiation of Co(acac)3. The present results were compared with those obtained by other authors.
On the Structure of Cobalt Garnet, a New Synthetic Silicate Containing 8-Coordinated Cobalt(II)
Authors: Sone Kozo , Ohashi Haruo
Published: July 2006

The X-ray structure of the CoO8 unit in cobalt garnet, a new synthetic silicate of the composition Co3Al2Si3O12, is presented. The unit can be taken as a deformed cube, but its central CoII is more regularly 8-coordinated than that in [Co(NO3)4]2− studied formerly by Bergman and Cotton. The electronic spectrum and magnetic moment of cobalt garnet are discussed in comparison with those of two other silicates containing CoO4 units.
Synthesis of Cytidine, Uridine, and Adenosine 5′-(2,6-Diamino-2,6-dideoxy-α-d-glucopyranosyl diphosphates)(Neosamine C-CDP, -UDP, and -ADP)
Authors: Tadano Kin-ichi , Tsuchiya Tohru , Suami Tetsuo , Rinehart Kenneth L
Published: July 2006

Three potential biosynthetic intermediates for aminocyclitol antibiotics, neosamine C-CDP, -UDP, and -ADP, have been synthesized from d-glucosamine by chemical means. 2,6-Diamino-2,6-dideoxy-α-d-glucopyranosyl phosphate, derived from the corresponding glycosyl bromide, was condensed with three nucleosides (CMP, UMP and AMP) by a known procedure. The configurations of the neosamine C nucleoside diphosphates have been confirmed by 13C NMR spectra.
Photoinduced Electron Transfer Oxidation. I. 9,10-Dicyanoanthracene-sensitized Photooxidation of Hindered Phenols
Authors: Futamura Shigeru , Yamazaki Kazuhiro , Ohta Hiroyuki , Kamiya Yoshio
Published: July 2006

9,10-Dicyanoanthracene (DCA)-sensitized photooxidation reactions of hindered phenols and catechols (1) proceed via the initial electron transfer from 1 to 1DCA*. 4-Hydroperoxy-2,5-cyclohexadien-1-ones and 4-hydroxy-2,5-cyclohexadien-1-ones are obtained from 2,4,6-trialkyl-substituted phenols, and an o-benzoquinone and furanone derivatives are afforded from 3,5-di-t-butylcatechol.
The Oxidation of the 2-Methyl Group of 3-Substituted 2-Methylindoles by Autoxidation and with Silver Acetate in Carboxylic Acids
Authors: Itahara Toshio , Ouya Hiroshi , Kozono Kiyotake
Published: July 2006

The autoxidation of 3-alkyl-2-methylindoles in carboxylic acids, such as propionic acid and acetic acid, at the reflux temperature resulted in the selective oxidation of the 2-methyl group and the formation of 3-alkyl-2-formylindoles. The formation of the 2-formylindoles was dependent on the nature of the solvent used. The treatment of 3-benzoyl-1,2-dimethylindole with silver acetate gave 2-acetoxymethyl-3-benzoyl-1-methylindole and 3-benzoyl-2-formyl-1-methylindole. The mechanistic implications for the autoxidation and the oxidation with silver acetate are presented.
Synthesis of Four Diastereoisomers of Histopine
Authors: Kitajima Yasuo , Waki Michinori , Izumiya Nobuo
Published: July 2006

Four isomers of histopine, N2-(1-carboxyethyl)histidine, were prepared to provide their physicochemical properties. A diastereomeric mixture, (RS),(S)-histopine (N2-[(RS)-1-carboxyethyl]-(S)-histidine), was synthesized from 2-oxopropionic acid and (S)-histidine by reduction with sodium cyanoborohydride. The mixture was separated into its components, (S),(S)-histopine and (R),(S)-histopine, by an ion-exchange column chromatography. In a similar manner (R),(R)-histopine and (S),(R)-histopine were prepared. Configurations of the four isomers obtained were assumed from their ORD data by comparison with those of the isomers of octopine (N2-(1-carboxyethyl)arginine) with a definite configuration.
Hydrates of Organic Compounds. VI. Heats of Fusion and of Solution of Quaternary Ammonium Halide Clathrate Hydrates
Authors: Nakayama Haruo
Published: July 2006

The heat of solution in water of four quaternary ammonium halide clathrate hydrates, R4NX·nH2O (R=n-C4H9, X=F and Cl, n=30; R=i-C5H11, X=F and Cl, n=39), and the heat of dilution of their aqueous solutions were measured calorimetrically. From these results, the heat of fusion of the clathrate hydrate solid (ΔHf) and the heat of solution of it in saturated solutions (ΔHsat) were obtained. The ΔHf was compared with a hypothetical heat of fusion of the same number of moles of ice I as the hydration number of the hydrate. The ΔHsat was about 14 kJ/mol smaller than the ΔHf in the (n-C4H9)4NX hydrates and about 27 kJ/mol smaller in the (i-C5H11)4NX hydrates irrespective of the type of anion. Furthermore, ΔHsat was calculated thermodynamically and it agreed with the calorimetrically obtained value within the experimental error.
The Crystal and Molecular Structure of Six-coordinate Intermediate-spin Porphinatoiron(III) Complex. (Octaethylporphinato)bis(tetrahydrofuran)iron(III) Perchlorate
Authors: Masuda Hideki , Taga Tooru , Osaki Kenji , Sugimoto Hiroshi , Yoshida Zen-ichi , Ogoshi Hisanobu
Published: July 2006

The crystal structure of (octaethylporphinato)bis(tetrahydrofuran)iron(III) perchlorate was determined by the X-ray method. The complex crystallizes in the monoclinic space group C2/m, a=13.916(3) Å, b=16.509(3) Å, c=10.659(5) Å, β=118.18(1)°, and Z=2. The structure was solved by the direct method and refined by the full-matrix least-squares method. The final R value was 0.079 for 597 reflections. The complex has a crystallo-graphically imposed twofold axis and a mirror of symmetry. The porphinato core is planar within 0.06 Å. The iron(III) ion lies at the center of the octahedron formed by the four porphinato nitrogen atoms and the two tetrahydrofuran oxygen atoms. The axial Fe–O distance, 2.187(11) Å, is considerably longer than the reported distances for high-spin porphinatoiron(III) complexes, while the equatorial Fe–N distance, 1.978(12) Å, is comparable to those for low-spin and intermediate-spin porphinatoiron(III) complexes. The Fe–O and Fe–N bond distances are well explained in terms of an intermediate-spin state of the iron(III) ion.
Facile Conversion of Thiosulfinic S-Ester to Sulfinic Ester
Authors: Takata Toshikazu , Oae Shigeru
Published: July 2006

Thiosulfinic S-testers are readily converted to the corresponding sulfinic eaters in good yields by treating in alcohols with a catalytic amount of I2, Br2, or HCl in the presence of H2O2, replacing sulfenyl groups by alcohols. The mechanism of this reaction is also discussed.
Catalytic Properties of Perovskite-type Mixed Oxides, La1−xSrxCoO3
Authors: Nakamura Teiji , Misono Makoto , Yoneda Yukio
Published: July 2006

The reactivity and related properties of oxygen both in the bulk and on the surface has been investigated for perovskite-type mixed oxides (La1−xSrxCoO3), in regard to the effects of Sr2+-substitution and calcination temperature. The reducibility and the readiness of oxygen desorption increased with the Sr2+ content, x, but the re-oxidation became slower with x. These results have been explained on the basis of the change in the chemical potential of lattice oxygen. The diffusivity of oxygen in the bulk and the ability to activate the oxygen molecule also increased with x. Oxygen vacancies in the bulk and on the surface, which tended to increase with x, are likely responsible for these reactions. The release of oxygen from the bulk became more difficult as the calcination temperature increased, in conformity with the trend of the catalytic activity.
Rearrangement of vic-Diol Monoacetates Promoted by Organoaluminium Compounds
Authors: Kanemoto Shigekazu , Morizawa Yoshitomi , Oshima Koichiro , Nozaki Hitosi
Published: July 2006

Treatment of pinacol monoacetate with organoaluminium reagent R3Al caused the rearrangement under uptake of R as a nucleophile on the resulting carbonyl carbon, while R2AlSPh produced the pinacolone itself upon workup.
Reinvestigation of the Pd-catalyzed Reaction of Azidoformate with Allylic Ethers
Authors: Migita Toshihiko , Chiba Mitsuo , Takahashi Katsuyuki , Saitoh Nobuhiro , Nakaido Setsuko , Kosugi Masanori
Published: July 2006

The most effective catalyst for leading reaction between azidoformate and allylic ethers to formation of 1-alkoxy-1-(alkoxycarbonylimino)alkane is PdCl2(PhCN)2; Pd(PPh3)4 can hardly show catalytic activity when pure reactants are employed.
The Crystal and Molecular Structure of Diaqua(tetraphenylporphinato)cobalt(III) Perchlorate
Authors: Masuda Hideki , Taga Tooru , Osaki Kenji , Sugimoto Hiroshi , Mori Masayasu
Published: July 2006

The crystal structure of diaqua(meso-tetraphenylporphinato)cobalt(III) perchlorate, [CoIII(tpp)(H2O)2]ClO4, has been determined by the X-ray method. The compound crystallizes in the monoclinic space group P21/c with four molecules in a unit cell of dimensions, a=13.93(4) Å, b=23.46(2) Å, c=17.35(6) Å, and β=129.4(2)°. The Co(III) ion lies on the mean plane of the porphinato core, and is coordinated by the four porphinato nitrogen atoms and the two water oxygen atoms. The average Co–N distance is 1.964(4) Å, and the average Co–O(water) distance is 1.936(5) Å. The porphyrin plane is significantly ruffled and has an approximate S4-\bar4 symmetry. The perchlorate anion is not bound directly to the cobalt(III) ion, and links the two adjacent [CoIII(tpp)(H2O)2]+ cations by the hydrogen bonds with the aqua ligand oxygen atoms.
Cation Interdiffusion in Polycrystalline Fluorite-cubic MgO–ZrO2 Solid Solution
Authors: Sakka Yoshio , Oishi Yasumichi , Ando Ken
Published: July 2006

Lattice and grain-boundary interdiffusion coefficients were calculated from the concentration distributions as determined for cation interdiffusion in polycrystalline MgO-stabilized zirconias by applying a grain-boundary enhanced diffusion model. Lattice interdiffusion coefficients in the temperature range of 1650–1990 °C were represented by \ ildeD=5.9×10−4exp [−293(kJ/mol)/RT] cm2/s. Magnesium self-diffusion coefficients were calculated from the obtained interdiffusion coefficients and the reported Zr self-diffusion coefficients. The results confirmed that interdiffusion in the fluorite-cubic solid solution is primarily controlled by the diffusivity of the faster cation.
Fluorometric Determination of Aluminium(III) and Cadmium(II) by Solvent Extraction of the Ternary Complex Composed of Metal Ion, 8-Hydroxy-5-quinolinesulfonic Acid, and Methyltrioctylammonium Ion
Authors: Kondoh Yukihiro , Kataoka Masamitsu , Kambara Tomihito
Published: July 2006

A fluorometric micro determination of aluminium(III) and cadmium(II) using the formation of metal–8-hydroxy-5-quinolinesulfonic acid–capriquat (methyltrioctylammonium) ternary complex is described. These complexes are easily extracted into chloroform phase and the extract emits a strong fluorescence. Spectra of aluminium(III) and cadmium(II) ternary complexes have the excitation maximum at 396 nm and 400 nm, and emission maximum at 501 nm and 524 nm, respectively. Fluorescence intensity of the aluminium(III) and cadmium(II) ternary complexes extracted into chloroform showed the constant and maximum values in the pH range of aqueous phase from 5.3 to 8.5 and 8.1 to 8.5, respectively. The calibration curves for aluminium(III) and cadmium(II) show good proportionality in the concentration range from 0.5 to 5.0 and 1.0 to 50.0 μg, respectively. The relative standard deviation observed with four measurements was found to be 1.8% for 0.5 μg of aluminium(III) and 1.1% for 10.0 μg of cadmium(II). The effect of diverse ions is studied and a 25-fold amount of Cu(II), Ni(II), Fe(II), Fe(III) in weight gave errors, however, the interferences were easily eliminated by the addition of appropriate masking agent. In the determination of cadmium(II), an equal amount of Co(II), Ni(II), Mn(II), Fe(III) and twice amount of Al(III) gave negative errors, however, the interference of Fe(III) and Al(III) were also eliminated as above.
The Vapor-phase Reaction of Aluminium Trichloride with Oxygen in the Presence of Steam and Properties of the Aluminium Oxide Formed
Authors: Shoji Yuichi , Matsuzaki Ryoko , Saeki Yuzo
Published: July 2006

The reaction of gaseous AlCl3 with oxygen containing 2–5 vol% H2O in the temperature range of 200 to 1000 °C, and the thermal transitions of the Al2O3 formed under various conditions were examined. At 200 °C, only the reaction of gaseous AlCl3 with H2O occurs, regardless of the H2O content in oxygen. Above about 400 °C, the reactions of gaseous AlCl3 with both H2O and oxygen occur, and all the AlCl3 reacts at 1000 °C. The reaction with H2O mainly occurs below about 900 °C, and the reaction with oxygen mainly occurs at 1000 °C. Regardless of the H2O content in oxygen, the reaction product is amorphous Al2O3 below 600 °C, amorphous Al2O3 containing poorly crystallized γ-Al2O3 at 800 °C, γ-Al2O3 containing amorphous Al2O3 at 900 °C, and a mixture of γ-Al2O3 and δ-Al2O3 at 1000 °C. It was also observed that the Al2O3 formed below 800 °C included a chloride oxide of aluminium. On heating the amorphous Al2O3 formed by the reaction of gaseous AlCl3 with oxygen containing 2–5 vol% H2O, the amorphous \xrightarrowca.700°Cχ\xrightarrowca.800°Cκ\xrightarrowca.1000°Cα transition occurs; on heating the γ-Al2O3 formed, the γ \xrightarrowca.900°Cδ \xrightarrowca.1000°Cθ \xrightarrowca.1000°Cα transition occurs.
The Crystal and Molecular Structure of (Acetylacetonato)(diacetylmethyl)(diethylamine)palladium(II)
Authors: Kurokawa Takahiro , Miki Kunio , Tanaka Nobuo , Kasai Nobutami
Published: July 2006

The molecular structure of [Pd(acac)2(NHEt2)] was determined by means of X-ray diffraction. The crystal belongs to the monoclinic system: a=14.166(1), b=8.209(1), c=14.764(2) Å, β=100.75(1)°, space group P21/n, with Z=4. The structure was solved by the heavy-atom method and refined anisotropically by the least-squares procedure; R=0.067 for 3149 non-zero reflections. The geometry around the Pd atom is square-planar: one of the two (acac) ligands coordinates to the Pd atom by O,O′-chelation, and the other, by σ-bonding of the γ-carbon atom, while the diethylamine occupies the fourth coordination site. A weak intramolecular N–H···O hydrogen bond [2.962(10) Å] is observed.
Stereochemistry of Bis[N-(2,6-diisopropylphenyl)salicylideneaminato]cobalt(II) Complexes
Authors: Yamada Shoichiro , Yamanouchi Kuniko
Published: July 2006

The compounds bis[N-(2,6-diisopropylphenyl)salicylideneaminato]cobalt(II) and analogous species with substituents at the 5-position of the salicyl moiety have been synthesized. They prefer the tetra-coordinate tetrahedral geometry in non-donor solvents, while some of them are forced into planar structures in the solid state. In pyridine, exclusively predominant species are five-coordinate complexes with the base bound with the cobalt(II) ion. Monopyridine adducts, which consist of five-coordinate complexes, have been isolated as crystals.
η3-2,4-Pentanedionato(2–) and Terminal-carbon-bonded β-Diketonato Complexes of Platinum(II)
Authors: Okeya Seichi , Nakamura Yukio , Kawaguchi Shinichi , Hinomoto Tetsu
Published: July 2006

A platinum(II)complex containing a 2,4-pentanedionate dianion as a trihapto ligand [Pt(acac(2–)-C1–C3){P(p-ClC6H4)3}2] was prepared by the reaction of [Pt(acac)2] with tris(p-chlorophenyl)phosphine and reacted with pyridinium perchlorate to afford [Pt(acac-C1)(py){P(p-ClC6H4)3}2](ClO4). A similar terminal-carbon-bonded complex of 1,1,1-trifluoro-2,4-pentanedionate monoanion with platinum(II) was also derived from [Pt(tfac(2–)C,O)(AsPh3)2] by the reaction with pyridinium perchlorate. These novel platinum(II) complexes were characterized mainly by IR and NMR spectroscopy.
Dinuclear Palladium(II) Complexes Containing Anilide Anions as Bridging Ligands
Authors: Okeya Seichi , Yoshimatsu Hisako , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

The reactions of [Pd(hfac)2] with aniline and its derivatives (L) in benzene at room temperature afforded [Pd(hfac)(hfac-C3)L], [Pd(hfac)L2](hfac), and [PdL4](hfac)2 depending on the reactants mole ratio. On the other hand, the reactions of various [Pd(β-dik)2] complexes with L in refluxing benzene (in most cases) gave rise to the aniline-bridged dinuclear complexes [Pd(β-dik)(L–H)]2, which in turn reacted with primary amines and pyridine (L′) to produce [PdL′2(L–H)]2(β-dik)2.
Selective Dimerization of Aldehydes to Esters Catalyzed by Hydridoruthenium Complexes
Authors: Ito Takashi , Horino Hiroshi , Koshiro Yoshitaka , Yamamoto Akio
Published: July 2006

RuH2(PPh3)4 and other hydridoruthenium complexes catalyze selective conversion of aldehydes into esters in high yields. The method is applicable to most aliphatic aldehydes as well as to aromatic aldehydes. The purity of aldehydes is critical for achieving high conversions, since the presence of carboxylic acid completely inhibits the reaction and alcohol and triphenylphosphine reduce the yields of esters. RuH2(PPh3)4 is converted into Ru(CO)3(PPh3)2 through the reaction indicating the occurrence of decarbonylation of aldehyde. A mechanism involving the acyl-H cleavage of aldehyde is proposed to account for the catalysis and formation of compounds accompanying the reaction. The mechanism is compared with an alternative one which comprises of consecutive insertions of two aldehyde molecules into Ru–H bond followed by β-hydrogen abstraction from an alkoxo intermediate formed. Addition of water changes the reaction course to give carboxylato carbonyl complexes Ru(OCOR)2(CO)m(PPh3)2 (m=1 and 2). Cross esterification studies showed the reactivity order of RCHO as R=Et>Me>n-Pr>i-Pr>>Ph.