A CNDO-type MO method of the third transition metal complexes and the electronic structure of methylmercury(II) halides.
スポンサーリンク
概要
- 論文の詳細を見る
The parameters of a CNDO-type SCF-MO method are determined for some 5d transition metal complexes such as IrCl<SUB>6</SUB><SUP>3−</SUP>, AuCl<SUB>4</SUB><SUP>−</SUP>, and HgCl<SUB>4</SUB><SUP>2−</SUP> by comparing the calculated transition energies of these complexes with their experimental values. MO calculations with these established parameters are also carried out for IrBr<SUB>6</SUB><SUP>3−</SUP>, AuBr<SUB>4</SUB><SUP>−</SUP>, HgX<SUB>4</SUB><SUP>2−</SUP>, HgX<SUB>2</SUB>, and CH<SUB>3</SUB>HgX (X=Cl, Br, and I). The transition energies and assignments obtained from MO calculations are in fair agreement with experimental ones, with a few exceptions. This MO method gives successful results for the electron density and the bond strength: (1) a linear relation is obtained between the calculated and observed net charges on the Hg atom of HgX<SUB>2</SUB> and CH<SUB>3</SUB>HgX, and (2) similar linear relations are obtained between the bond index <I>E</I><SUB>M–X</SUB> values and the stretching force constant <I>f</I><SUB>M–X</SUB> and between the <I>E</I><SUB>Hg–C</SUB> value and the <I>f</I><SUB>Hg–C</SUB>. Some discussion is presented for the Hg–C bonding character of the CH<SUB>3</SUB>HgX; the Hg–C bond is mainly contributed from the covalent interaction of the 6s and 6p orbitals of the Hg atom with the 2s and 2p orbitals of the C atom. The contributions of the Hg 5d orbitals and the electrostatic interaction are rather small.
- 公益社団法人 日本化学会の論文
著者
-
SAKAKI Shigeyoshi
Department of Applied Chemistry & Biochemistry, Faculty of Engineering, Kumamoto University
-
Iwasaki Noriko
Department Of Otorhinolaryngology Kanazawa Medical University
-
Ohyoshi Akira
Department Of Applied Chemistry Faculty Of Engineering Kumamoto University
-
Sakaki Shigeyoshi
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
-
Hagiwara Nobuo
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
-
Iwasaki Noriko
Department of Chemistry, Faculty of Science, Kumamoto University
-
Iwasaki Noriko
Department of Industrial Chemistry, Faculty of Engineering, Kumamoto University
関連論文
- Theoretical Study of the Iron Sulfur Cluster-free Hydrogenase (Hmd) : What is the Active Center of Hmd?
- Detection of Potential Molecular Recognition Ability in Linear Poly (methyl acylate)
- Enhancement of Diastereomer Selectivity Using Highly-Oriented Polymer Stationary Phase
- Formation of the Oxanickelacyclopentene Complex from Nickel(0), Carbon Dioxide, and Alkyne. An ab initio MO/SD-CI Study. Part II.^ Reactivity and Regioselectivity of Hydroxyacetylene
- Valproic Acid-induced Hearing Loss and Tinnitus
- 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
- Photoinduced Deracemization of [Co(acac)_3] (acac-=acetylacetonate) with Chiral *-[Ru(menbpy)_3]^ (menbpy=4, 4'-bis {(1R, 2S. 5R)-(-)-menthoxycarbonyl}-2, 2'-bipyridine)
- High Enantioselectivity in the Electron Transfer Reaction between a Ru(II) Complex of Menbpy Anion Radical, [Ru(menbpy)_3] + [menbpy=4,4'-di{1R, 2S, 5R)-(-)-menthoxycarbonyl}-2, 2' - bipyridine] and [Co(acac)_3] : A Pulse Radiolysis Study
- Photoasymmetric Synthesis of [Co (edta)] ^- from Co (II) Salt and L_4edta (L=H^+ or Na^+), Using a Chiral Cu (I) Complex
- Charge Effects in Photoinduced Electron-Transfer Reactions between [Ru(bpy)_3]^2+ and Viologen Derivatives
- A Theoretical Study on the Oxidative Addition of a Si-H σ-Bond to [MCl(CO)(PH_3)_2](M=Rh or Ir). Similarities to and Diffrences from [M'(PH_3)_2](M'=Pd or Pt) and [RhCl(PH_3)_2]
- 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
- Semi-empirical SCF–MO Studies of Platinum Hydrides and the Insertion Reaction of Ethylene into the Pt(II)–H Bond
- 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.
- MO Calculation for Interactions of Cu(II) and Co(III) with Hydroperoxides
- 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 and Thermochromic Properties of New Five-coordinate Copper Chelates
- 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.
- Homogeneous isomerization of 1-butene catalyzed by [MX2(PR3)2]-NaBH4 systems (M=Co, Ni, X=halides, SCN, PR3=PPhnEt3-n) - Acceleration by phosphine addition and stereoselectivity.
- Vibrational Spectra and Normal Coordinate Analysis of Bis(methylthio)mercury