Thermal stability of alkylcopper(I) complexes coordinated with tertiary phosphines.
スポンサーリンク
概要
- 論文の詳細を見る
Thermolysis of isolated alkylcopper(I) complexes having tertiary phosphine ligand(s) RCuL<I><SUB>n</SUB></I> (R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>, <I>i</I>-C<SUB>4</SUB>H<SUB>9</SUB>) in the solid state and in toluene has been studied in order to clarify the role of the tertiary phosphine ligand in stabilizing the alkylcopper(I) complexes. The distribution of the thermolysis products shows that the thermolysis of the alkylcopper complexes having ethyl or longer alkyl chain proceeds through a β-elimination mechanism. The rate of the thermolysis obeys the first order rate law, −d[RCuL<I><SUB>n</SUB></I>]/d<I>t</I>=<I>k</I>[RCuL<I><SUB>n</SUB></I>]. The activation parameters of the thermolysis were obtained from the temperature dependence of <I>k</I> and a compensation effect between Δ<I>H</I><SUP>\neweq</SUP> and Δ<I>S</I><SUP>\neweq</SUP> was demonstrated. The activation energy <I>E</I><SUB>a</SUB> of the thermolysis of RCu(PPh<SUB>3</SUB>)<SUB>2</SUB> increases in the order of R=C<SUB>2</SUB>H<SUB>5</SUB><<I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB><<I>i</I>-C<SUB>4</SUB>H<SUB>9</SUB>. Coordination of electron-donating tertiary phosphine decreases <I>E</I><SUB>a</SUB> and a linear relationship between ν(Cu–CH<SUB>3</SUB>) frequencies and <I>E</I><SUB>a</SUB> for thermolysis of the methylcopper complexes was observed. Addition of PPh<SUB>3</SUB> into the toluene solutions of CH<SUB>3</SUB>Cu(PPh<SUB>3</SUB>)<SUB>2</SUB>(diethyl ether)<SUB>0.5</SUB> and C<SUB>2</SUB>H<SUB>5</SUB>Cu(PPh<SUB>3</SUB>)<SUB>2</SUB> causes some retardation of the thermolysis. The major role of the tertiary phosphine ligand in stabilizing the alkylcopper complexes is proposed to strengthen the Cu–C bond by changing the electronic state of copper atom. An energetic consideration based on Chatt and Shaw's theory is given in order to account for the results concerning the stabilities of the alkylcopper complexes. Photolysis of the alkylcopper complexes takes a quite different decomposition pathway producing mainly RH from RCuL<I><SUB>n</SUB></I>.
- 公益社団法人 日本化学会の論文
著者
-
Yamamoto Takakazu
Research Laboratory Of Resouces Utilization Tokyo Institute Of Technology
-
Yamamoto Akio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
-
Miyashita Akira
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
-
Yamamoto Takakazu
Research Laboratory of Resourecs Utilization, Tokyo Institute of Technology
関連論文
- Solvents and Molecular Weights of Nitrated Poly(p-phenylene)and Poly(pyridine-2, 5-diyl)
- Photo Chemical Vapor Deposition of Metal Oxide Films Relating to Bi-Sr-Ca-Cu-O Superconductor
- Purification and UV-VIS Light Absorption Property of Source Materials for CVD of High-T_c Superconducting Films
- Ni-Promoted Syntheses of New 3, 3'-Dichloro-5, 5'-bipyrazoles and Poly(bipyrazole-5, 5'-diyl)s and Isolation of Nickel Complexes Relevant to the Syntheses
- Kinetic Study of Ligand Exchange Reactions of Bis(1, 5-cyclooctadiene)nickel(0) with 2, 2'-Bipyridine, 4, 4'-Dimethyl-2, 2'-bipyridine, and 4, 4', 5, 5'-Tetramethyl-2, 2'-bipyridine
- Curing Reactions of Bismaleimidodiphenylmethane with Mono- or Di-functional Allylphenols. High Resolution Solid-State ^C NMR Study
- Thermal Reactions of N-Phenylmaleimide and Mono- or Di-functional Allylphenols
- Curing Reactions of Bismaleimide Resins Catalyzed by Triphenylphosphine. High Resolution Solid-State ^C NMR Study
- Control of Reductive Elimination and Acidolysis of Diarylnickel(II) Complexes by the Kind of Bronsted Acid and the Presence of Oxygen
- N-(ベンジリデンアミノ)ピロール類の電気化学的特性と重合.導電性高分子の新しいモノマー(E)
- Synthesis of New Polypyrroles by Oxidative Polymerization of N-(Benzylideneamino)pyrrolea and Properties of the Polymers
- Light Emitting Properties of Linear π-Conjugated Poly(arylene)s
- Thermal Isomerization of mer-[RhH(SAr)(SiHAr'_2)(PMe_3)_3] to fac-[RhH_2{SiAr'_2(SAr)}(PMe_3)_3] Involving Thiolato Group Transfer from Rh to Si
- Preparation of New Poly (phenylene vinylene) Type Polymers by Ni-promoted Polycondensation and Their Photoluminescent Properties
- Preparation of Poly(diphenylamine-4,4'-diyl)and a Related Polymer by Organometallic Polycondensation and Their Properties
- Dichroism of π-Conjugated Poly (quinoxaline-5,8-diyl) s in Stretched Poly (vinyl alcohol) Film and Photoluminescence of the Polymer
- π-Conjugated Polymers Prepared by Organometallic Polycondensation
- Chemical and Electrochemical Preparation of Poly(quinoline-2,6-diyl), Poly(quinoxaline-2,6-diyl), and Poly(1,5-naphthyridine-2,6-diyl)by Using Nickel Complexes. Importance of the 2,6-Bonding for Linear Structure, Highly Extended π-Conjugation, and Strong
- Preparation and Properties of Highly Electron-accepting Poly(pyrimidine-2,5-diyl)
- Linear Structure and Viscometric and Electrical Properties of Nitrated Poly (p-phenylene)s
- Soluble Copolymers of p-Phenylene and m-Phenylene. Their Basic Properties
- Enhancement of Third-Order Optical Nonlinearity of Poly (aryleneethynylene) s by Introducing an Intramolecular Charge Transfer Interaction into Their π-Conjugation
- π-Conjugated Charge Transfer Polymer Constituted of Electron-donating Thiophene and Electron-withdrawing Quinoxaline
- Poly(pryidine-2,5-diyl) Contaning Indigo Unit and Optical Third Harmonic Generation from Its Film
- Excimer-Type Electroluminescence and Carrier-Transporting Properties of Electron-Accepting π-Conjugated Polymers
- Preparation of a New π-Conjugated Polymer Chelating Ligand, Poly (2,2'-bipyridimidine-5-5'-diyl), and Its Metal Complexes
- Comparison of Packing Modes of Poly (thiophene)s and Poly (thiazole)s
- Intermolecular π-π Interraction of Poly (4, 4'-dialkyl -2, 2'-bithiazole - 5, 5'-diyl) s and Photoluminescence of the Polymers
- Polymer Light-Emitting Diodes with Single- and Double-Layer Structures Using Poly(2,3-diphenylquinoxaline-5,8-diyl)
- Preparation of New π-Conjugated Poly(2, 3-diphenylquinoxaline-5, 8-diyl) and Poly(2, 3-di(p-tolyl)-quinoxaline-5, 8-diyl). Electrochemical Activity and Light-emitting Diode
- Preparation of ^C-Poly(p-phnylene). IR, ^C-NMR, and ESR Spectra of the Polymer
- Preparation and Properties of New π-Conjugated Poly(benzimidazole-4,7-diyl) and Poly(2,1,3-benzothiadiazole-4,7-diyl)
- New Type of π-Conjugated Polymers Constituted of Quinone Units in the Main Chain
- Preparation of Poly(3-alkoxythiophene-2,5-diyl)s by Organometallic Process and Doping-Undoping Behaviors of the Polymers
- Preparation of Cu(I)Complexes with N-Bonded or O-Bonded p-Cyanophenoxido Ligand and Their Structures in Solid State in Solution
- Si-H and Si-C Bond Activation of a Triorganosilane Promoted by[RhCl{P(i-Pr)_3}_2]. Synthesis and Structure of a Dinuclear Rh(IV) Complex with μ-Silylene Ligands
- Stacking of Poly(3-alkylthiophene)s and Poly(4-alkythiazole)s in a Colloidal Solution and in the Solid
- Iodine Doing of Poly (Thiophene-2,5-diyl) and Poly (3-aikythiophene-2,5-diyl)s in Aqueous Media
- Redox Behavior of Poly(diphenylamine-4,4'-diyl) in Acidic Aqueous Media and Electronic Properties of the Doped Polymer
- 1 : 2 Polycondensation of 3,3',4,4'-Biphenyltetramine and 1,1'-Ferrocenedimethanol Catalyzed by [RuCl_2(PPh_3)_3] to Give Polybenzimidazole Containing Ferrocenylene Groups
- Cyclodextrin Complexes of Bisepoxide and of α, ω-Diamine in Several Molar Ratios. Preparation and Characterization in the Solid State
- Preparation of α,ω-Diols of Long Carbon Chains and Their Use in Polyurethane Synthesis
- Kinetic Results and Reaction Pathways of Intermolecular Thiolato Ligand Migration Between Titanocene Complexes and from Cp_2 Tix(SAr)(X=Cl, SAr) to PtCl(Me)(cod)(cod=η^2,η^2-1,5-Cyclooctadiene)
- Synthesis of π-Conjugated Soluble Poly(aryleneethynylene) Type Polymers and Their Properties
- Strong Dichroism of π-Conjugated Poly(2,2'-bipyridine-5,5'-diyl) and Poly(pyridine-5,2-diyl-thiophene-2,5-diyl) in Stretched Poly(vinyl alcohol) Film
- Preparation and Properties of Poly(methylpyridine-2,5-diyl)s
- X-Ray Analysis of Poly (thiophene-alt-thiophene-1,1-dioxide)
- Colloidal Solution of Poly(3-hexylthiophene-2,5-diyl) in Mixtures of Chloroform and Methanol and Alignment of the Polymer in Stretched Poly(ethylene terephthalate) Film. Investigation for Intermolecular Interaction and Alignment of the Polymer
- Preparation of Electrically Conducting Polyanilines by a New Method and Electrical Conducting Properties of the Polymers
- Molecular Assembling of π-Conjugated Poly (pyrimido [5,4-d] pyrimidine-2,6-diyl) s Prepared by Organometallic Polycondensation
- Random π-Conjugated Copolymers Constituted of Electron-donating Thiophene Units and Electron-accepting Pyridine Units
- Electrochemical Behavior of Electrodes Modified with π-Conjugated Polymers in 0. 5 M H_2SO_4(aq) and 1M KOH(aq) Electrolytes
- Synthesis of Ru- and Os-Complexes of π-Conjugated Oligomers of 2, 2'-Bipyridine and 5, 5'-Bipyrimedine. Optical Properties and Catalytic Activity for Photoevolution of H_2 from Aqueous Media
- Molecular Orientation in Vacuum-Deposited Poly(thiophene) Film Studied by Second-Harmonic Generation
- ポリ(アントラキノン)類の電気化学的還元ポテンシャルとモノマ-ユニットの電子親和力の関係
- Preparation of New Main-chain Type Polyquinone and Its Properties
- Preparation and Properties of π-Conjugated Poly(1,10-phenanthroline-3,8-diyl)
- Poly (thiophene-2,5-diyl) Having Crown Ethereal Subunit. Preparation, Stable n-Doped State, and Light Emitting Diode
- Heterojunctions Obtained Using Semiconducting Metal Sulfide-Polymer Composite Films
- Alkaline Metal Secondary Batteries Using Poly(2,5-pyridinediyl) as an Active Electrode Material
- Electrochemical Deposition of Films of p-Doped Regioregular Poly(3-hexylthiophene-2, 5-diyl)
- Preparation of New Main-Chain-Type Polyquinones and Their Electrochemical Response
- Rate of Exchange of NH Hydrogen of Polyaniline, Poly(1-naphthylamine), and Diphenylamine with H_2O Hydrogen on NMR Time Scale
- π-Conjugated Polymers Bearing Electronic and Optical Functionalities. Preparation by Organometallic Phlycondensations, Properties, and Thier Applications
- N-Oxidation of π-Conjugated Poly (heterocycle) s Containing Nitrogen and Electrically Conducting Properties of the N-Oxidized Products
- Determination of Optical Constants of Polyquinoxalines as Electroluminescent Materials
- Insertion of carbon monoxide into nickel-alkyl bonds of monoalkyl- and dialkylnickel(II) complexes, NiR(Y)L2 and NiR2L2. Preparation of Ni(COR)(Y)L2 from NiR(Y)L2 and selective formation of ketone, diketone, and aldehyde from NiR2L2.
- Crystal and molecular structure of (ethyl methacrylate)-bis(triphenylphosphine)nickel(0).
- Oxidative addition of esters of formic acid and .BETA.-lactones to Ni(0)-complexes involving cleavage of the C-O bond.
- Kinetics and Stoichiometry of Nitrogen Fixation with TiCl3-Mg and VCL3-Mg in Tetrahydrofuran
- Preparation of copper(I)-phosphine complexes having Cu-N bonds and their reactions with organic halides.
- Preparation of organic copper(I) complexes by the reactions of methylbis(triphenylphosphine)copper(I) with nitroalkanes, .BETA.-diketones, and cyanoalkanes.
- Trans-esterification reaction catalyzed by alkoxo(triphenylphosphine)copper(I) complexes.
- Synthesis, reactions and catalytic properties of stable alkoxocopper, phenoxocopper and related copper complexes containing triphenylphosphine ligands.
- Bis(2,4-pentanedionato)phenylchromium(III). Preparation and reactions with organic carbonyl compounds and alcohols.
- Preparation and Properties of Methylcopper-triphenylphosphine Complexes
- Reactions of CO2 with Cu(I) alkoxides and amides to give alkylcarbonato-, .MU.-carbonato-, hydrogencarbonato-, and carbamato-copper complexes.
- Formation of adducts of poly(thienylene)s with electron acceptors and electric conductivities of the adducts.
- Preparation of alkylnickel(II)-phosphine complexes by reactions of Ni(acac)2 with alkylaluminums in the presence of tertiary phosphine.
- Dialkylpalladium(II) complexes. Syntheses, characterizations, and reactions with CO, I2, and CH3I.
- Transition metal alkoxides. Preparation and properties of bis(aryloxo)iron(II) and bis(alkoxo)iron(II) complexes having 2,2'-bipyridine ligands.
- Dynamic behavior of acetylacetonato, triphenylphosphine and alkyl ligands in NiR(acac)(PPh3)n (R=C2H5, CH3) in solution and disproportionation of the alkylnickel complexes in pyridine.
- Alteration of reaction course in thermolysis of cis-diethylbis(tertiary phosphine)palladium(II) from reductive elimination to .BETA.-elimination process induced by addition of tertiary phosphine ligand.
- Study of organo(2,2'-bipyridine)nickel complexes. III. NMR studies on the interaction of dialkyl(2,2'-bipyridine)nickel with solvents and olefins.
- Polymerizationn of Vinyl Compounds by Dihydridotetrakis-(triphenylphosphine)ruthenium(II)
- Preparation and properties of monoalkylnickel(II) complexes NiR(NR1R2)L2 having imido,imidazolato,or methyl phenylcarbamato-N ligand.
- Palladium catalyzed C-C coupling for synthesis of .PI.-conjugated polymers composed of arylene and ethynylene units.
- Resonance Raman and 129I Moessbauer spectroscopic study of iodine doped in poly(thienylene)s.
- The Mechanism of Vinyl Polymerization by Dialkylbis(dipyridyl)iron(II)
- Preparation and properties of nickel-phosphine complexes coordinated with .ALPHA.,.BETA.-unsaturated ester.
- Preparation and properties of monoalkylnickel(II) complexes having a phenoxo, benzenthiolato, oximato, .BETA.-diketonato, or halo ligand.
- Mechanisms of thermal decomposition of trans- and cis-dialkylbis-(tertiary phosphine) palladium(II). Reductive elimination and trans to cis isomerization.
- Reactions of dialkylnickel(II) complexes NiR2L2 with alkyl (or aryl) halides, R'COY (Y=Cl,Br,OPh,OCOPh), and CS2.
- Thermal stability of alkylcopper(I) complexes coordinated with tertiary phosphines.
- A novel type of polycondensation utilizing transition metal-catalyzed C-C coupling. I. Preparation of thermostable polyphenylene type polymers.
- Reversible CO insertion into an Ni-C bond of alkyl(acetylacetonato)-(triphenylphosphine)nickel(II).