• 제목/요약/키워드: Triphenylphosphine

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Triphenylphosphine Phenylimide의 전기화학적인 환원 (Electrochemical Reduction of Triphenylphosphine Phenylimide)

  • 박종민
    • 대한화학회지
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    • 제18권5호
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    • pp.341-353
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    • 1974
  • Triphenylphosphine phenylimide의 비수용액에서의 전기화학적인 환원반응을 polarography, cyclic voltammetry, controlled-potential coulometry 및 electron spin resonance 법을 써서 고찰하였다. 이 유기인화합물은 one-electon transfer에 따라서 anion radical이 형성되나 순간일 뿐이고 protonation과 재차 one-electon reduction 결과 인과 질소사이의 이중결합이 끊어진다. 그 결과 아닐린이 주요 반응생성물로서 발견되었다. 또 한편 동반하는 화학반응결과 생긴 주산물의 하나인 triphenylposphine oxide의 환원결과 인과 페닐 사이의 단일결합이 끊어지는 것도 관찰할 수 있었다.

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전하전이착체형 잠재성 촉매를 사용한 반도체 성형용 자소성 에폭시 수지 시스템의 경화 반응속도 연구 (Cure Kinetics of Self-Extinguishing Epoxy Resin Systems with Charge Transfer Complex Type Latent Catalyst for Semiconductor Encapsulation)

  • 김환건
    • 반도체디스플레이기술학회지
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    • 제13권4호
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    • pp.27-32
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    • 2014
  • The cure properties of self-extinguishing epoxy resin systems with different charge transfer type latent catalysts were investigated, which are composed of YX4000H as a biphenyl epoxy resin, MEH-7800SS as a hardener, and charge transfer type latent catalysts. We designed and used five kinds of charge transfer type latent catalyst and compared to epoxy resin systems with Triphenylphosphine-Benzoquinone(TPP-BQ) as reference system. The cure kinetics of these systems were analyzed by differential scanning calorimetry with an isothermal approach, the kinetic parameters of all systems were reported in generalized kinetic equations with diffusion effects. The epoxy resin systems with Triphenylphosphine-Quinhydrone(TPP-QH), Triphenylphosphine-Benzanthrone(TPP-BT) and Triphenylphosphine-Anthrone(TPP-AT) as a charge transfer type latent catalyst showed a cure conversion rate of equal or higher rate than those with TPP-BQ. These systems with TPP-QH and Triphenylphosphine-Tetracyanoethylene(TPP-TCE) showed a critical cure reaction conversion of equal or higher conversion than those with TPP-BQ. The increases of cure conversion rates could be explained by the decrease of the activation energy of these epoxy resin systems. It can be considered that the increases of critical cure reaction conversion would be dependent on the crystallinity of the biphenyl epoxy resin systems.

Structure and Reactivity in the Reaction of Diazoindanes and Diazoindanones with Triphenylphosphine : The Formation of Mono-, and Bisphosphazines and Hydrazone-Compounds

  • 성대동;강동효;류준하
    • Bulletin of the Korean Chemical Society
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    • 제18권9호
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    • pp.945-952
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    • 1997
  • The reactions of diazoindanes and diazoindanones with triphenylphosphine have been studied in acetonitrile. The diazoindanes and diazoindanones react with triphenylphosphazine. The reaction of 1,3-bis(diazo)indan-2-one with a tenfold excess of triphenylphosphine in dry acetonitrile gave the 1,3-bis(phosphazino)indan-2-one, however in acetonitrile containing below of 1% water, the 1,3-bis(hydrazono)indan-2-one was produced by hydrolysis. The phosphazine compound could be easily converted into bishydrazone by recrystallization, due to small amounts of water in the solvent. The reactivity of triphenylphosphine toward diazoindanes and diazoindanones depends on the structrue of the diazo compounds.

Mechanistic Studies on the Oxidation of Triphenylphosphine by $[(tpy)(bpy)Ru^{IV}=O]^{2+}$, Structure of the Parent Complex $[(tpy)(bpy)Ru^{II}-OH_2]^{2+}$

  • 석원경;김미영;Yoshinobu Yokomori;Derek J. Hodgson;Thomas J. Meyer
    • Bulletin of the Korean Chemical Society
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    • 제16권7호
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    • pp.619-624
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    • 1995
  • Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

The Comparative Study in the Oxygen Atom Transfer Reaction by Ruthenium Mono-Oxo Complexes

  • Seok, Won K.;Son, Yung J.;Moon, Sung W.;Lee, Heung N.
    • Bulletin of the Korean Chemical Society
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    • 제19권10호
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    • pp.1084-1090
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    • 1998
  • The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

Synthesis of 2,7-Methano-aza[10]annulene Derivatives

  • 김충섭
    • Bulletin of the Korean Chemical Society
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    • 제17권5호
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    • pp.437-442
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    • 1996
  • Electrocyclic ring-closure of 6-vinylcyclohepta-1,3,5-isocyanate has been carried out in the presence of triphenylphosphine to examine a catalyzing effect of the triphenylphosphine. The preparation of 10-(1-carboalkoxyalkyl)-2,7-methanoaza[10]annulenes by the electrocyclic ring-closure of ketenimine intermediates, which are formed by the reaction of triphenylalkylidenephosphorane and 6-vinylcyclo-hepta-1,3,5-isocyanate, is described. 10-Alkyl-2,7-methanoaza[10]annulenes were prepared by basic hydrolysis of the carboalkoxyaza[10]annulenes and decarboxylation of the acid intermediates. In the same manner, 10-(N-alkyl(or aryl))-2,7-methanoaza[10]annulenes were prepared from the reaction of the isocyanate and N-alkyl(or aryl)iminotriphenylphosphorane via electrocylic ring-closure of carbodiimide intermediate.

New ETL 층에 의한 저전압 구동 백색 발광 OLED (Low Voltage Driving White OLED with New Electron Transport Layer)

  • 문대규
    • 한국전기전자재료학회논문지
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    • 제22권3호
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    • pp.252-256
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    • 2009
  • We have developed low driving voltage white organic light emitting diode with a new electron transport material, triphenylphosphine oxide ($Ph_{3}PO$). The white light emission was realized with a rubrene yellow dopant and blue-emitting DPVBi layer. The new electron transport layer results in a very high current density at low voltage, resulting in a reduction of driving voltage. The device with a new electron transport layer shows a brightness of $1150\;cd/m^2$ at a low driving voltage of 4.3 V.