bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetics of Liquid-phase Hydrogenation of Aliphatic α,β-Unsaturated Aldehyde over Raney Cobalt Catalyst
Authors: Hotta Kazuhiko , Kubomatsu Teruo 
Published: July 2006

Abstract
Kinetic studies on the hydrogenation of 2-methyl-2-pentenal (UD) over the Raney cobalt catalyst were performed at temperatures ranging from 10 to 40°C in n-hexane. The products were found to be 2-methylpentan-1-ol (SA), 2-methyl-2-penten-1-ol (UA) and 2-methylpentanal (SD). The initial rates of the formation of SA(rSA), SD(rSD), and UA(rUA) were determined in the concentrations of UD(CUD), 0.026–0.263 mol/l. It was found by kinetic analysis that (rSA+rSD) was represented by a Langmuir-type rate equation and rUA by another one. The rate equations which fitted the rate data are as follows.
r SA+rSD=\frac1.1×1010e−15200⁄RTCUD(1+4.4×105e−7500⁄RTCUD)2
r UA=\frac1.2×108e−13500⁄RTCUD(1+9.3×103e−5600⁄RTCUD)2
A mechanism in which the formation of SA and SD and that of UA proceed through different types of adsorbed UD was proposed. The adsorbed species in enol form and that in keto form were considered with respect to the formation of SA and SD. Activation energies for the formation of SA plus SD and of UA were determined to be 7.7 and 7.9 kcal/mol, respectively. The selectivity defined as the ratio of rSA to (rSA+rSD) was found to increase with the increase of the surface coverage of hydrogen.
Thiocyanoacetate. I. Reactions of Thiocyanoacetic Esters with Aldehydes
Authors: Kambe Satoshi , Hayashi Toshio , Yasuda Heinosuke , Midorikawa Hiroshi 
Published: July 2006

Abstract
Thiocyanoacetic esters (I) and aldehydes reacted in the presence of potassium fluoride or carbonate to give α,β-unsaturated ester as a major product and an unexpected solid product (II) as a minor one, which was determined to be N-carbamoyl-2-imino-5-substituted 1,3-oxathiolane-4-carboxylic esters.
Formation of Ketenimines by the Reaction of Thioamides with Diethyl Azodicarboxylate and Triphenylphosphine
Authors: Mitsunobu Oyo , Kato Koki , Wada Makoto 
Published: July 2006

Abstract
The reaction of diphenylacetothioanilide with diethyl azodicarboxylate and triphenylphosphine gave rise to the formation of diphenylketene(N-phenyl)imine. Similarly, the reaction of N-(p-tolyl)diphenylacetothioamide gave diphenylketene(N-p-tolyl)imine. On treatment with diethyl azodicarboxylate in the presence of sodium ethoxide, diphenylacetothioanilide afforded bis(N-phenylbenzalimidoyl) disulfide in a good yield. The intermediate of the formation of the ketenimines is also discussed.
The Reactions of Aroyl Peroxides with Grignard Reagents. III. On the Structure and the Reaction of the Complex Containing Benzoyl Peroxide
Authors: Okubo Masao , Maruyama Kazuhiro , Osugi Jir\={o} 
Published: July 2006

Abstract
The orange-colored complex which is formed in the reaction of benzoyl peroxide with Grignard reagent was studied by infrared spectra, and the reaction of the complex with Grignard reagent was also examined. In this complex, the structure of BPO was still maintained by coordinating with magnesium atom through the peroxidic as well as the carbonyl oxygen atoms. Reaction products of this complex with phenylmagnesium bromide were benzoic acid(as Mg-salts), phenyl benzoate, benzophenone, triphenylcarbionol, and bromobenzene. The heterolytic mechanism on the formation of bromobenzene was proposed. The molar ratio of products depended seriously upon the mode of addition of Grignard reagents. The exclusive formation of bromobenzene and Mg-salts of benzoic acid without phenyl benzoate under an experimental condition was explained by assuming the electron-transfer process through the coordinating bond in the complex.
Liquid Phase Chlorination of Olefins with Cupric Chloride. III. Effect of Additives and Kinetics
Authors: Koyano Takashi , Watanabe Osamu 
Published: July 2006

Abstract
Chlorination of 1-octene with cupric chloride has been investigated in methanol at 110–130°C. The yield of 1,2-dichlorooctane (I) increased by addition of lithium chloride in the reaction mixture, while that of 1-chloro-2-methoxyoctane (II) decreased. Addition of water and cuprous chloride markedly retarded the reaction. The initial rates of formation of I and II could be expressed as v=k[octene]0 [CuCl2]01.6 and v=k[octene]0 [CuCl2]0, respectively. These results can be explained as an initial formation of a complex between olefin and cupric chloride molecule, followed by competitive attack on the complex by chloride ion and methanol. In the less polar reaction media containing more octene, the ratio of I/II increased. This may be ascribed to the steric effect of cupric chloride in the intermediate.
Studies on Reactions of Isoprenoids. XIV. Facile Lactone Formations from 2-endo-Cyano-, 2-endo-Cyanomethyl-, and 2-endo-Carboxymethyl-5-norbornenes
Authors: Sasaki Tadashi , Eguchi Shoji , Sugimoto Michio 
Published: July 2006

Abstract
Treatment of 2-endo-cyano-5-norbornene (I) with polyphospholic acid (PPA) at 60°C afforded 6-endo-hydroxybicyclo[2.2.1]heptane-2-endo-carboxylic acid lactone (V) in 40–46% yields, while 2-endo-cyanomethyl-5-norbornene (IV) prepared from 2-endo-methoxycarbonyl-5-norbornene (II) via the corresponding alcohol (III) gave 3-exo-hydroxybicyclo[2.2.1]heptane-2-exo-acetic acid lactone (VIII) in 25% yield by a similar treatment with PPA. With sulfuric acid, IV gave only intractable polymeric materials. However, under milder conditions using a sulfuric acid-acetic acid mixture, IV afforded 2-exo-cyanomethyl- (VI) and 2-exo-carbamoylmethyl-6-exo-acetoxynorbornane (VII) in 69 and 2% yields, respectively. On the other hand, iodolactonization of the carboxylic acid (IX) derived from IV afforded 5-exo-iodo-6-endo-hydroxybicyclo[2.2.1]heptane-2-endo-acetic acid lactone (X) in 68% yield. The formation of VIII from IV was explained by the successive Wagner-Meerwein rearrangement, 3,2- and 6,2-hydride shifts, followed by cyclization.
A Modification of Red Blood Cells by Isocyanates
Authors: Kitajima Masao , Sekiguchi Wataru , Kondo Asaji 
Published: July 2006

Abstract
Modified red cells that have a reinforced membrane and hemoglobin which is difficult to denature are prepared by treating red cells with some isocyanates. These modified cells have the same shape as normal red cells, but they are not lysed by osmotic pressure or by the actions of any reagents except for some ionic surface-active agents. No agglutination was observed when they were mixed with the blood of foreign animals or with blood of different blood groups. The hemoglobin within the cell gave a reversible oxygenation curve and had a high oxygen affinity. Toluene-2,4-diisocyanate was found to be the most suitable reagent among the many isocyanates examined. A suspension reaction method which consists of the addition of an isocyanate emulsion to a red-cell suspension at 5°C is developed for the modification process.
The Synthesis of the Polymer Containing the Si-O-phenylene Bond, using Transition Metal Salts as Catalysts
Authors: Iwakura Yoshio , Uno Keikichi , Toda Fujio , Hattori Kenjiro , Abe Minoru 
Published: July 2006

Abstract
Various transition metals were found to be effective as catalysts in the dehydrocondensation of phenols and silanes.
R3SiH+PhOH\oversetmetal salt→R3SiOPh+H2
The effective species were PdCl2, H2PtCl6·6H2O, PtCl2, RhCl3, NiCl2, silane-treated NiCl2, Ptl2, PtS, Raney Ni, Pd-black, Pt-black, Au-black, FeCl3, ZnCl2, CuSO4, CuCl, Cu–Cr, Cu(CH3CO2)·CuO, the methyl ethyl ketoxime complex of Pd, Pt(OX)3, and Pd(OX)2. The ineffective species were metal mirrors of Pd, Au, Ag, Pt, and Cu, and the acetylacetonato complex of Ni, Co(II), Co(III), and Cu. The reaction was then extended to the preparation of polymers containing a Si–O–phenylene linkage in the main chain. Dihydricphenols, e.g., bisphenol A, hydroquinone, 4,4′-dihydroxydiphenyl gave high-molecular-weight polymers with an equimolar amount of a dihydro-silane, e.g., diphenylsilane, p-toluylmethylsilane and p-bisdimethylsilylphenylene, in bulk or in a solvent at temperatures above 150°C. The polymer obtained began to flow above 100°C.
Radikalische aromatische m-Nitrierung bei Umsetzung von Benzoylperoxyd mit Stickstoffdioxyd und bei Umsetzung von p-Chlorperoxybenzoesäure mit Stickstoffoxyd in Toluol
Authors: Suehiro Tadashi , Hirai Mikio , Kaneko Takehira 
Published: July 2006

Abstract
Die radikalische Nitrierung des Toluols findet bei der Umsetzung von Benzoylperoxyd mit Stickstoffdioxyd bei 60–100°C in 4–15% Ausbeute und bei der Umsetzung von p-Chlorperoxybenzoesäure mit Stickstoffoxyd bei 20–80°C in 30–50% Ausbeute statt. In beiden Umsetzungen waren die Isomeren-Verhältnisse der gebildeten Nitrotoluole o/m/p=6–25/75–91/0–3. Daß diese m-orientierende Nitrierung über das Zwischenprodukt, Aroyloxycyclohexadienyl-Radikal, abläuft, wurde sichergestellt aufgrund der Isomeren-Verhältnisse der Nitrotoluole im Vergleich zu denen der Benzoesäureester von Kresolen aus der konkurrierenden Benzoyloxylierung (o/m/p=40–54/13–16/33–45) und aufgrund der relativen Reaktivität des Toluols (2–4) gegenüber Benzol bei der Nitrierung und der Benzoyloxylierung.
The Synthetic Intermediate of Pyridoxine. II. The Thermal Cyclization of Ethyl α-Isocyanopropionate to 5-Ethoxy-4-methyloxazole
Authors: Maeda Itsutoshi , Togo Kazushi , Yoshida Ryonosuke 
Published: July 2006

Abstract
The thermal cyclization of ethyl α-isocyanopropionate (I) was performed to 5-ethoxy-4-methyloxazole (II) as an intermediate for the synthesis of pyridoxine. The similar reaction of several new alkyl esters of α-isocyanocarboxylic acid to the corresponding 5-alkoxy-4-substituted oxazole was also carried out. The reaction products of the thermal cyclization of I were investigated. When the cyclization was carried out at 180°C for 5 hr, the maximum yield of the main product, II, was 20%; unreacted I (30%), ethyl α-cyanopropionate(20%), and dimer of I (5%) were also obtained. The α-hydrogen of ethyl α-isocyanosuccinate (X) can be more easily removed than that of I, so X may be expected to be more readily converted to 5-ethoxy-4-ethoxycarbonylmethyloxazole (XI), which is also an intermediate of pyridoxine. The yield of XI from X did not exceed 30% because of the side reaction.
Studies on Intermolecular Complex Formation. I. Between Nucleotide Bases and Organic Compounds
Authors: Tamura Chihiro , Sakurai Noriko , Sato Sadao 
Published: July 2006

Abstract
The present investigation was focussed on a survey of the chemical compounds which are capable of binding with nucleotide bases. X-Ray powder patterns show that adenine and cytosine have a strong tendency to interact with many organic compounds having a carboxyl group and cyclic alternant CONH groups. A few compounds bind with thymine and uracil.
The Hybridization Effect on the Equilibrium Distance. III
Authors: Miyazaki Tomoo , Shigetani Tsunehisa , Shinoda Hiroyuki 
Published: July 2006

Abstract
In order to re-examine the unexpected conclusion previously reported that the hybridization effect is unimportant in determining the C–C single bond length, a more reliable calculation involving the configuration interaction treatment and more elabolate calculations by the NDDO and unrestricted INDO methods have been performed. The results of the INDO-CI and unrestricted INDO calculations were in good agreement with those which were obtained by the previous calculations. According to the NDDO calculations, however, the equilibrium distances of different kinds of C–C single bonds were found to increase with the decreased s character in hybrids, although this effect was not very significant. The effect of interaction between non-adjacent atomic orbitals in determining the bond length has been discussed in full detail.
The Protonation of Aromatic Hydrocarbon Radical Anions. I. A Comparison of Methods and a Study of the Mechanism
Authors: Hayano Shigeo , Fujihira Masamichi 
Published: July 2006

Abstract
The protonation mechanism of the aromatic hydrocarbon radical anions, such as biphenyl, naphthalene, phenanthrene, anthracene, 1,2-benzanthracene, and pyrene, in dimethylformamide (DMF) and water mixtures was studied. Three methods of measuring the concentration of the radical anions, i.e. polarography and ESR and UV absorption spectroscopy, were compared with each other by making simultaneous measurements of the same anthraquinone radical anion solution. A good linear relation of the polarographic anodic diffusion current to the UV absorbance was found, while the ESR signal intensity had linear relations with neither of the others in the system which contained an excessive number of parent molecules, 2×10−3m. The change in the visible absorption spectra of the aromatic hydrocarbon radical anions as a function of the time suggested that all the aromatic hydrocarbon radical anions decay by a first-order reaction. As a result, the radical anions were considered to decay through the following sequence:
R\ewdot+H2O\oversetk→RH·+OH−, RH·+R\ewdot\ightleftharpoonsRH−+R, and RH−+H2O\oversetk′→RH2+OH−.
The Solubilization of Orange OT in Anionic Surfactant Solutions: A Polarographic Study
Authors: Hayano Shigeo , Shinozuka Noriko 
Published: July 2006

Abstract
Orange OT (1-o-tolyl-azo-β-naphthol) solubilized in sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) solutions showed a well-defined irreversible polarographic wave. The proportionality of the limiting current to the square root of the mercury height and to the dye concentration indicates the wave to be diffusion-controlled. It is noted that the anionic surfactants showed the waves due to the adsorption-de-sorption and reorientation of the surfactant molecules on the electrode. The apparent diffusion coefficients of the solubilized dye calculated from the polarographic data were in good agreement with those of the anionic surfactant micelle with electrolyte. We may conclude that the polarographic diffusion coefficient of the solubilized dye is equal to that of the micelle of the solubilizer surfactant. The marked surfactant concentration dependence of the diffusion coefficient was observed with both surfactants and was attributed to the interaction of the micelles. The transfer coefficient of the electrode reaction of Orange OT increased with an increase in the concentration of the surfactant. This tendency is different from the effect of the surface-active agents on the transfer coefficient in the reduction of inorganic ions. From the experimental observations, it seems that the electrode reaction of the solubilized dye is little effected by the charged micelles.
Proton Spin-Lattice Relaxation Studies of Intermolecular Interactions in the Mixtures of Chloroform and Proton-Acceptor Solvents
Authors: Sato Kazuo , Nishioka Atsuo 
Published: July 2006

Abstract
Proton spin-lattice relaxation measurements were carried out on chloroform in carbon tetrachloride, benzene, pyridine, acetone, and dimethylsulfoxide (DMSO) in order to investigate the effect of the intermolecular interaction on the spin-lattice relaxation time, T1 of chloroform. It was found that the order of the effects of solvents on T1 is as follows: DMSO&gt;acetone, pyridine&gt;benzene, carbon tetrachloride; this order corresponds to that of the association constant of chloroform with these solvents. The T1 values of benzene and acetone were also determined on chloroform-benzene and chloroform-acetone mixtures. On the basis of the results obtained on these solutions together with the results on the T1 of chloroform in various solvents, we estimated the lifetimes of the chloroform-benzene complex and of the chloroform-acetone hydrogen-bonding complex. We tried to keep the proton-density constant throughout the solutions, in order to avoid an ambiguity arising from its change, by adopting the corresponding deuterated compounds.
Studies of Seven-Membered Heterocyclic Compounds Containing Nitrogen. X. Syntheses of 5,6,8,9-Tetrahydro-7H-pyrimido[4,5-d]azepines
Authors: Yamamoto Hiroshi , Nakata Masaru , Morosawa Shiro , Yokoo Akira 
Published: July 2006

Abstract
5,6,8,9-Tetrahydro-7H-pyrimido[4,5-d]azepine and some of its derivatives were synthesized. 6-Acetyl-3-hydroxy-4,5,7,8-tetrahydro-6H-pyrazolo[3,4-d]azepine was also synthesized.
The Reactions of Photogenerated Solvated Electrons in Methanolic Solutions of Potassium Iodide
Authors: Seki Hiroshi , Imamura Masashi 
Published: July 2006

Abstract
Hydrogen formation from UV-irradiated potassium iodide solutions was studied using CH3OH and CH3OD as the solvents and nitrous oxide and acids as the solvated-electron scavengers. The maximum quantum yield of the solvated electron in CH3OH was found to be 0.6 both in nitrous oxide and in acid solutions. It was concluded that the solvated electron produces hydrogen in pure methanol through Reaction (1), e−solv→H+CH3O−, with a quantum yield of 0.35 at 25°. The rate constant of this reaction is 5.4×105sec−1, corresponding to a half-life of 1.3 μsec. From the results obtained with acid solutions, it was also concluded that nitrous oxide reacts with a solvated electron to produce one molecule of nitrogen in neutral methanol.
Preparation of Chromium(III) and Cobalt(III) Complexes with d,l-α-Phenylalanine-N,N-diacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The following chromium(III) and cobalt(III) complexes with PADA (d,l-α-phenylalanine-N,N-diacetic acid) were prepared: K[Cr(OH)pada(H2O)]·5H2O (violet) (I), K[Cr(OH)pada(H2O)2]·3H2O (green)(II), (enH2)1⁄2[Cr(OH)pada(H2O)2] (green) (III), [Cr pada(o-phen)]·H2O (brown) (IV), K2[Cr(ox)pada]·2H2O (violet) (V), K[Co(OH)pada(H2O)]·5H2O (blue-violet) (VI), and K2[Co2(OH)2(pada)2] (brown-pink) (VII). On the basis of electronic spectra in both aqueous solution and solid state, it was found that PADA behaves toward central metal as a quadridentate ligand in complexes I, IV, V, VI, and VII; in other words, unlike the case of nitrilotriacetic acid (NTA), nitriloisopropionicdiacetic acid (NIPDA) and l-leucine-N,N-diacetic acid (LDA), PADA did not give different coordinating structures to the respective complexes in solid state and aqueous solution. From thermal analysis with derivatograph in the reaction processes of complex VI, it was found that the complex liberates one mole of coordinating water at about 170–180°C, resulting in the formation of the diol complex VII.
Studies on Cobaloxime Compounds. IV. The Polarography of Cobaloximes
Authors: Hohokabe Yorikatsu , Yamazaki Noboru 
Published: July 2006

Abstract
Various types of cobaloximes, e.g., Co-alkyl derivatives with different bases as an axial ligand and polymeric cobaloximes with the general formula of Co(OH)(DH)2(Copoly—AM-VPy) (DH: dimethylglyoximato monoanion) in which Copoly—AM-VPy is a low-molecular-weight copolymer of acrylamide and 4-vinylpyridine, were prepared, and their half-wave potentials in cathodic reduction were compared to each other and to those of a few vitamin B12 compounds. All of them showed a single irreversible cathodic wave. Methyl- and cyano-cobaloximes were reduced at more negative potentials than the corresponding methylcobalamin and cyanocobal-amin(vitamin B12). The half-wave potential of methylcobaloxime shifted in the direction of the more negative potentials as the donating strength of the axial base increased. This was correlated with the charge-transfer transition energies of those cobaloximes as determined from their electronic spectra. The polymeric cobaloximes were reduced at less negative potentials than the others.
Several Novel Ru(VI) and Ru(IV) Complexes Derived from [RuO4bipy] and [RuO3phen]2O
Authors: Ishiyama Toshio 
Published: July 2006

Abstract
Five novel neutral complexes of ruthenium(VI) and ruthenium(IV) with 2,2′-bipyridine and 1,10-phenanthroline, [RuO2(OH)2bipy]·3H2O, [Ru(OH)3phen]2O, [RuO2bipy2]·3H2O, [RuO2bipy·phen]·3H2O and [RuO2phen2], were prepared and characterized by a study of their infrared, visible and ultraviolet absorption spectra, and by polarographic measurements. [RuO2(OH)2bipy] and [Ru(OH)3phen]2O were obtained by the reduction of previously-reported complexes, [RuO4bipy] and [RuO3phen]2O respectively, with methanol, and [RuO2bipy2], [RuO2bipy·phen] and [RuO2phen2], by the reactions of [RuO4bipy] and [RuO3phen]2O in methanol with 2,2′-bipyridine and 1,10-phenanthroline respectively. [RuO2bipy·phen] and [RuO2phen2] were also obtained in methanol by the substitution reactions of [RuO2bipy2] and [RuO2bipy·phen] with 1,10-phenanthroline respectively. The five complexes were all diamagnetic. [RuO2(OH)2bipy] was assumed to be a “ruthenyl” complex with two oxide ions coordinated at the trans positions, like such well-known trans-dioxoruthenyl analogues as Cs2[RuO2Cl4] and [RuO2(OH)2(NH3)2], and [Ru(OH)3phen]2O was assumed to be a binuclear complex with an oxygen-bridge between ruthenium atoms. [RuO2bipy2], [RuO2bipy·phen], and [RuO2phen2] were assumed to be mononuclear complexes with two oxide ions coordinated at the trans positions, and their oxidation numbers were found polarographically, to be 4.
The Chemical-transport Reaction of Spinel-type Oxides
Authors: Nagasawa Koichi , Bando Yoshichika , Takada Toshio 
Published: July 2006

Abstract
Single crystals and thin films of spinel-type oxides were prepared by a chemical-transport reaction in a closed system, using HCl gas as the transport agent. This paper will report on the preparation conditions and the reaction process of the chemical-transport reaction. The reaction process of Co3O4 was found to be different from that of other oxides, since Co3O4 was dissociated into CoO and O2 in the closed tube. The reaction process was explained by the difference in the dissociated oxygen pressure between the source zone and the crystallization zone in the system. The chemical-transport reaction of NiFe2O4 was applied to the preparation of thin film. The single-crystal thin films were epitaxially grown on the (110) and (111) surfaces of MgO.
The Effect of Axial Pyridine Ligands on the Charge Transfer Bands of trans-Bis(dimethylglyoximato)Cobalt(III) and -Iron(II) Complexes
Authors: Yamano Yukio , Masuda Isao , Shinra Koichiro 
Published: July 2006

Abstract
The electronic absorption spectra of [CoIII(dmgH)2B2]+ and [FeII(dmgH)2B2] (dmgH=dimethylglyoximate monoanion and B=pyridine derivatives) are inspected with respect to the effect of the axial pyridine ligands on the charge-transfer bands of the complexes. The characteristic bands observed in the 275–305 mμ region for the Co(III) complexes and in the 485–555 mμ region for the Fe(II) complexes, which have been assigned to a metal→oxime charge-transfer band, are shifted to shorter wavelengths with a decrease in the basicity of the pyridine derivatives. The results have been discussed by taking into account the π-interaction of the dπ(dxz, dyz) orbital of the central metal ion with the empty π-orbitals of both the dimethylglyoximate and the pyridine derivatives. It is suggested that the π-interaction is stronger in the Fe(II) complexes than in the Co(III) complexes, while the σ-bond is stronger in the latter. The infrared spectral evidence that the C=N stretching frequency is dependent on the axial pyridine derivatives, and that it is observed at a lower frequency in the Fe(II) than in the Co(III) complexes, is consistent with the above results.
Kinetics and Mechanism of the Ligand Substitution Reaction of the Mercury(II)-4-(2-pyridylazo)resorcinol Complex with 1,2-Cyclohexanediamine-N,N,N′,N′-tetraacetic Acid
Authors: Funahashi Shigenobu , Tabata Masaaki , Tanaka Motoharu 
Published: July 2006

Abstract
Kinetics and mechanism of the ligand substitution reaction of the mercury(II)-PAR complex with CyDTA were studied at 25°C in the presence of halogenide ion at an ionic strength of 0.1. The rate law can be written as
−\fracd[Hg(par)22−]dt=(k1′[H+]+k2′+k3,X′[H+][X−])\frac[Hg(par)22−][Hpar−][Hcydta3−]
where X− refers to a halogenide ion (chloride, bromide, iodide). The rate constants k1′, k2′, and k3,X′ were determined as: k1′=(2.4±0.1)×107 m−1 sec−1, k2′=(1.9±0.1)×10−2 sec−1, k3,Cl′=(4.5±0.2)×109 m−2 sec−1, k3,Br′=(3.2±0.1)×1011 m−2 sec−1, k3,I′=(5.6±0.2)×1014 m−2 sec−1. The rate constants for the paths involving mixed hydroxo and halogeno complexes (k2′ and k3,X′) are quantitatively accounted for in terms of electron donation of ligands OH− and X−.