The thermochemical behavior of pentaamminedinitrogenruthenium(II) complexes and the kinetics of the liberation of ammonia from the complex in the solid state.
スポンサーリンク
概要
- 論文の詳細を見る
The thermochemical reactions of [Ru(NH<SUB>3</SUB>)<SUB>5</SUB>N<SUB>2</SUB>]X<SUB>2</SUB> (X=Cl, Br, I) were investigated in the solid state. The ammonia ligand was liberated at a lower temperature (165–213 °C) than the nitrogen ligand (243–270 °C). The isothermal measurement reveals that the first step of the degradation of the complex can be expressed as: [Ru(NH<SUB>3</SUB>)<SUB>5</SUB>N<SUB>2</SUB>]X<SUB>2</SUB>(s)→[RuX(NH<SUB>3</SUB>)<SUB>4</SUB>N<SUB>2</SUB>]X(s)+NH<SUB>3</SUB>(g) (X=Cl, Br, or I). The rate of the reaction is first-order to [Ru(NH<SUB>3</SUB>)<SUB>5</SUB>N<SUB>2</SUB>]X<SUB>2</SUB>, and the first-order rate constant increased in the order of: chloride<bromide<lodide. The activation energies and the activation entropies (<I>E</I>/kJ mol<SUP>−1</SUP> and <I>ΔS</I><SUP>\neweq</SUP>/J K<SUP>−1</SUP> mol<SUP>−1</SUP> respectively) for the reaction were as follows: chloride (181±1,62±1), bromide (99±1, −95±2), and iodide (89±1, −102±3). The values of <I>ΔS</I><SUP>\neweq</SUP> suggest that the salt with Cl<SUP>−</SUP> degrades through an <I>S</I><SUB>N</SUB>l-like mechanism, while those with Br<SUP>−</SUP> and I<SUP>−</SUP> degrade through an <I>S</I><SUB>N</SUB>2-type mechanism. The thermochemistry of [Ru(NH<SUB>3</SUB>)<SUB>5</SUB>N<SUB>2</SUB>]X<SUB>2</SUB> has been discussed on the basis of the strong π-backbonding ability of the nitrogen ligand and the electronegativity of the outer-sphere ions.
- 公益社団法人 日本化学会の論文
著者
-
Itoh Noriko
Department Of Human Environmental Sciences School Of Human Environmental Sciences Mukogawa Women&apo
-
Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
-
Kawaguchi Hitoshi
Department Of Electrical And Information Engineering Yamagata University
-
Kohata Susumu
Yatsushiro College of Technology
関連論文
- Role of matrix metalloproteinase-7 in angiogenesis associated with age-related macular degeneration
- Cloning and molecuar characterization of calpain, a calcium-activated neutral proteinase, from different strains of Schistoma japonicum
- Crystal Structure of a 6-Hydroxynaphtho［2，1-b］-3H-1，4-thiazin-2（1H）-one Derivative
- Formation of Naphtho [2, 1-b]-3H-1, 4-thiazin-2 (1H)-one Derivatives by Reactions of 4-Arylazo-1-naphthols with Mercaptocarboxylic Acids
- Feasibility of Observing a Spin Drag Effect in the Electronic Transport
- Supercontinuum Generation and Pulse Compression in Short Fibers for Optical Pulses Generated by 1.5 μm Optical Parametric Oscillator
- Anomalous Critical Temperature over 200 K in Multiphase Tl-Ba-Ca-Cu-O System
- Doping Effects of Metallic Elements on the Superconductivity in the Tl-Ba-Ca-Cu-O System
- Doping Effects of Metallic Elements on the Superconductivity in the Bi-(Pb)-Sr-Ca-Cu-O System
- Polarization-Dependent Optical Gain and Gain Saturation in Vertical-Cavity Surface-Emitting Lasers
- Crystal structure of (chloro(tris((1-ethyl-1H-benzimidazol-2-yl)-methyl)amine)zinc(II)) tetraphenylborate acetone.
- Studies of the Ruthenium(III) Complex. V. Aquation and Anation Reactions of Halogenoacetatopentaammineruthenium(III) Complexes in Aqueous Solutions
- Studies of Ruthenium Complexes. VIII. Kinetic Studies of the Thermal Substitution Reaction of Hexaammine and cis-Dihalogenotetraammineruthenium(III) Complexes in the Solid State
- Studies of the ruthenium(III) complexes. XII. Kinetic studies of the deammonation-anation reactions of halogenopentaammineruthenium(III) complexes in the solid state.
- Response of a copper(II) ion-selective electrode in cupric buffers based on macrocyclic polyamines.
- Synthesis and characterization of a chloro-bridged binuclear iron(III) complex.
- Synthesis and Reactions of Titanoxycarbene-Metal Carbonyl Complexes.
- The thermochemical behavior of pentaamminedinitrogenruthenium(II) complexes and the kinetics of the liberation of ammonia from the complex in the solid state.
- Studies of Ruthenium Complexes. VII. Photochemical Reactions of cis-Dihalogenotetraammineruthenium(III) Complexes in Aqueous Solutions
- Studies of Ruthenium Complexes. IV. The Solvent Effect on the Isotopic Ligand-exchange Reaction of the cis- Dibromotetraammineruthenium(III) Complex
- Studies of the ruthenium complexes. XI. The reaction mechanism of the base hydrolysis of halogenopentaammineruthenium(III) complexes.
- Synthesis and characterization of imidazolate-bridged trinuclear (copper(II)-manganese(II)-copper(II)) complexes.
- Synthesis and characterization of substituted derivatives of (tetraazacycloalkadienato)nickel(II) complexes with uniegative ligands, and crystal structure of parent complex (Ni(Me2(14)dienatoN4))BrH2O.
- Synthesis, characterization, and crystal structure of substituted derivatives of (tetraazacyclotetradecatetraenato)copper(II) complexes.
- A CNDO-type MO method of the third transition metal complexes and the electronic structure of methylmercury(II) halides.
- Halogenation of mixed ligand cobalt(III) complexes with 12- or 13-membered tetraaza macrocycle and acetylacetone, (Co(Z)aneN4(acac))(ClO4)2 (Z=12,13).
- The electronic structure of Ru(III)-ammine complexes and the product distribution from solid-state thermal reaction.
- Studies of Ruthenium Complexes. III. Kinetics of Isotopic Ligand-Exchange Reactions of Halogenopentaammineruthenium(III) Complexes in Aqueous Solution
- Synthesis, magnetic property, and crystal structure of imidazolate-bridged manganese(III)-copper(II) dinuclear complex.
- Studies of the ruthenium complexes. XIII. Kinetic studies of electron-transfer reactions between aquapentaammineruthenium(II) and halopentaammineruthenium(III) comlexes.