• Title/Summary/Keyword: Triphenylphosphine

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Electrochemical Reduction of Triphenylphosphine Phenylimide (Triphenylphosphine Phenylimide의 전기화학적인 환원)

  • Pak Chong Min;Wilson M. Gulick, Jr.
    • Journal of the Korean Chemical Society
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    • v.18 no.5
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    • pp.341-353
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    • 1974
  • The electrochemical reduction of triphenylphosphine penylimide in nonaqueous media has been examined by polarography, cyclic voltammetry, controlled-potential coulometry and electron spin resonance spectroscopy. The reduction of triphenylphosphine phenylimide proceeds by a one-electron transfer to form anion radical which undergoes both protonation and a second one-electron reduction followed by cleavage of the phosphorus-nitrogen double bond. Aniline is a major product. The cleavage of a phosphorus-phenyl bond was also observed after reduction of triphenylphosphine oxide which is one of the major products of the chemical reaction which follow the primary process.

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

  • Kim, Whan Gun
    • Journal of the Semiconductor & Display Technology
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    • v.13 no.4
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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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    • v.18 no.9
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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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    • v.16 no.7
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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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    • v.19 no.10
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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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    • v.17 no.5
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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.

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

  • Moon, Dae-Gyu
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.22 no.3
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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.