• Title/Summary/Keyword: Chemical hydride

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Polarity of freestanding GaN grown by hydride vapor phase epitaxy

  • Lee, Kyoyeol;Auh, Keun-Ho
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.11 no.3
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    • pp.106-111
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    • 2001
  • The freestanding GaN substrates were grown by hydride vapor phase epitaxy (HVPE) on (0001) sapphire substrate and prepared by using laser induced lift-off. After a mechanical polishing on both Ga and N-surfaces of GaN films with 100$\mu\textrm{m}$ thick, their polarities have been investigated by using chemical etching in phosphoric acid solution, 3 dimensional surface profiler and Auger electron spectroscopy (AES). The composition of the GaN film measured by AES indicted that Ga and N terminated surfaces have the different N/Ga peak ratio of 0.74 and 0.97, respectively. Ga-face and N-face of GaN revealed quite different chemical properties: the polar surfaces corresponding to (0001) plane are resistant to a phosphoric acid etching whereas N-polar surfaces corresponding to(0001) are chemically active.

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Electronic and Bonding Properties of BaGaGeH: Hydrogen-induced Metal-insulator Transition from the AlB2-type BaGaGe Precursor

  • Kang, Dae-Bok
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.153-158
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    • 2012
  • The hydrogenation of $AlB_2$-type BaGaGe exhibits a metal to insulator (MI) transition, inducing a puckering distortion of the original hexagonal [GaGe] layers. We investigate the electronic structure changes associated with the hydrogen-induced MI transition, using extended H$\ddot{u}$ckel tight-binding band calculations. The results indicate that hydrogen incorporation in the precursor BaGaGe is characterized by an antibonding interaction of $\pi$ on GaGe with hydrogen 1s and the second-order mixing of the singly occupied antibonding $\pi^*$ orbital into it, through Ga-H bond formation. As a result, the fully occupied bonding $\pi$ band in BaGaGe changes to a weakly dispersive band with Ge pz (lone pair) character in the hydride, which becomes located just below the Fermi level. The Ga-Ge bonds within a layered polyanion are slightly weakened by hydrogen incorporation. A rationale for this is given.

Efficient Preparation of 3-Fluoropyrrole Derivatives

  • Kim, Bo-Mi;San, Quan-Ze;Bhatt, Lok Ranjan;Kim, Sung-Kwon;Chai, Kyu-Yun
    • Bulletin of the Korean Chemical Society
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    • v.31 no.1
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    • pp.31-34
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    • 2010
  • Noble N-substituted-3-fluoropyrroles derivatives were prepared from new precursor via ring formation. The addition reaction of ethyl iododifluoroacetate to vinyl trimethylsilane under the Cu(0) catalyst resulted in the formation of ethyl-2,2-difluoro-4-iodo-4-(trimethylsilyl)butanolate, which reacted with diisobutylaluminium hydride at $-30^{\circ}C$ to yield 2,2-diflouro-4-iodo-4-(trimethylsilyl)butanal. Finally, a series of N-substituted-3-fluoropyrrole derivatives were synthesized by the reaction of 2,2-diflouro-4-iodo-4-(trimethylsilyl)butanal with $NH_4OH$ or primary amines followed by reaction with KF solution.

Enantioselective Reduction of Racemic Three-Membered Heterocyclic Compounds. 3. Reaction of Epoxides with B-Isopinocampheyl-9-borabicycolo[3.3.1]nonane-Potassium Hydride and Potassium B-Isopinocampheyl-9 boratabicyclo[3.3.1]nonane Systems$^1$

  • Cha, Jin-Soon;Lee, Kwang-Woo;Yoon, Nung-Min
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.421-423
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    • 1987
  • The chiral B-isopinocampheyl-9-borabicyclo[3.3.1]nonane-potassium hydride (IPC-9-BBN-KH) and potassium B-isopinocampheyl-9-boratabicyclo[3.3.1]nonane (K IPC-9-BBNH) systems were applied to the enantioselective reduction of representative racemic epoxides, namely 1,2-epoxybutane, 1,2-epoxyoctane, 3,3-dimethyl-1,2-epoxybutane and styrene oxide. In the case of IPC-9-BBN-KH system, the optical yields are in the range of 8.3-37.4$\%$ ee. However, the system of K IPC-9-BBNH provides significantly lower optical yields, showing 7-22.5$\%$ ee. These results strongly suggest that the enantioselective coordination of chiral organoborane to the epoxy oxygen of racemic epoxides plays an important role in this resolution.

Enantioselective Synthesis of 1-Substituted 1,2,3,4-Tetrahydroisoquinoline Alkaloids via Asymmetric Reduction

  • Byung Tae Cho;Cheol Kyu Han
    • Bulletin of the Korean Chemical Society
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    • v.12 no.5
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    • pp.565-569
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    • 1991
  • Enantioselective synthesis of 1-substituted tetrahydroisoquinoline alkaloids (1) via asymmetric reduction of 1-substituted 3,4-dihydroisoquinolines (2) and the corresponding iminium salts (3) with the selected chiral hydride reagents, such as K glucoride (5), Itsuno's reagent (6), and Mosher's reagent (7) were examined. In these reactions, dihydroisoquinolines were not reduced by the hydride reagents, whereas the iminium salts were easily reduced under the same reaction conditions found in successful reduction of ketones. Thus, the reduction of 6,7-dimethoxy-3,4-dihydroisoquinolium iodide(3a) with 5, 6 and 7 provided the product 1a with 52.3 % ee, 18 % ee, and 66.4 % ee, respectively. For 1-benzyl derivatives (3b-3d), syntheses of 1b-1d with 0.7-6.2 % ee, 5.9-21 % ee, and 1.4-2.7 % ee were achieved with chiral reducing agents 5, 6 and 7, respectively. For 1-aryl derivatives, use of 5, 6 and 7 resulted in optical inductions in the range of 25.2-43 % ee, 13-21.1 % ee, and 6.3-16 % ee, respectively.

Homogeneous Catalysis (VI). Hydride Route with Chloro Ligand Dissociation for the Hydrogenation of Acrylonitrile with trans-Chlorocarbonylbis(triphenylphosphine)iridium(I)

  • Moon, Chi-Jang;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.4 no.4
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    • pp.180-183
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    • 1983
  • The reaction of $IrClH_2(CO)(Ph_3P)_2$ ($Ph_3P$=triphenylphosphine) with acrylonitrile (AN) produces a stoichiometric amount of propionitrile (PN) at $100^{\circ}C$ under nitrogen, which suggests that the catalytic hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ proceeds through the hydride route where the formation of the dihydrido complex, $IrClH_2(CO)(Ph_3P)_2$ is the initial step. The rate of the hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ is decreased by the presence of excess $Cl^-$ in the reaction system, which suggests that $Cl^-$ is the dissociating ligand in the catalytic cycle. It has been also found that the rate of the hydrogenation increases with inercase both in hydrogen pressure and in concentration of free $Ph_3P$, and with decrease in AN concentration in the reaction system.

MO Studies on the Gas-Phase Reaction of Dypnone Oxide with Chloride Ion$^\dag$

  • Kim, Wang-Ki;Sohn, Chang-Kook;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.7 no.4
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    • pp.279-282
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    • 1986
  • The MNDO calculations were performed in order to investigate the gas-phase reaction mechanism of 2-propene-1-al oxide, as a model compound of dypnone oxide(1,3-diphenyl-2-butene-1-one oxide) with the chloride ion. Optimized geometries and heats of formation for two probable concerted pathways, CHO and H migration, were determined and their activation energies were obtained. MO results show that although the formyl migration is thermodynamically more favorable than the hydride migration, the latter kinetically predominates over the formyl migration, which is contrary to the established migrating preferences. It is concluded that the hydride migratory propensity is catalyzed by the chloride ion by reducing the capability of the carbonyl ${\pi}$ bond to participate in the migration.

A Study on the Synthesis of Titanium Carbonitride by SHS(Self-propagating High-temperature Synthesis) Method (자체반응열 고온합성법을 이용한 Titanium Carbonitride의 합성에 관한 연구)

  • Ha, Ho;Hwang, Gyu-Min;Lee, Hee-Cheol
    • Journal of the Korean Ceramic Society
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    • v.31 no.6
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    • pp.637-642
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    • 1994
  • Using SHS(Self-propagating High-temperature Synthesis) method, the optimum synthetic condition of titanium carbonitride was established by controlling the parameters such as relative density of mixture (Ti+C), nitrogen pressure, additive amounts of titanium hydride(TiH1.924) and protecting heat loss. Under 1 atm nitrogen pressure, nitridation ratio with changing relative density of the sample compacts has a maximum (87.2%) at about 55%, and in the case of enveloping the pellet with a quartz tube, the highest nitridation ratio of 90% was obtained at about 68%. At relative density of 55%, nitridation ratio with the nitrogen pressure has a miximum (87.3%) at 7 atm. As the amounts of additive titanium hydride increased, nitridation ratio decreased at below 7 atm nitrogen pressure and, increased at above this pressure until percent of addition percent reached 15 wt% and decreased abruptly upon futher increases in titanium hydride. In the synthesis of TiCxNy by combustion reaction, heat transfer from combustion zone to preheating zone and nitrogen gas penetration into the compact were found to be important factors affecting the TiCxNy formation. It was difficult to obtain high nitridation ratio when the conbustion temperature was either too high or too low, and it seems that the retention of high temperature after a combustion wave sweeped through the reactant mixture pellet is critical to obtain a satisfactory nitridation ratio.

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