• Title/Summary/Keyword: $CH{_3}^+$

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Iridium(Ⅲ) Complexes of η$^6$-Arenes with Olefinic and Cyclopropyl Substituents: Facile Conversion to η ³-henylallyl Complexes

  • 정현목;주광석;진종식
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.402-405
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    • 1997
  • Olefinic and cyclopropyl group substituted arenes (C6H5Y) react with [Cp*Ir(CH3COCH3)3]A2 (A=ClO4-, OTf-) to give η6-arene complexes, [Cp*Ir(η6-C6H5Y)]2+ (1a: Y=-CH=CH2 (a),-CH=CHCH3 (b),-C(CH3)=CH2 (c),-CH-CH2-CH2 (d)). Complex 1b-1d are readily converted into η3-allyl complexes, [Cp*(CH3CN)Ir(η3-CH(C6H5)CHCH2)]+ (2a) and [Cp*(CH3CN)Ir(η3-CH2(C6H5)CH2)]+ (2b), in the presence of Na2CO3 in CH3CN. The η6-styrene complex, 1a reacts with NaBH4 to give η5-cyclohexadienyl complex, [Cp*Ir(η5-C6H6-CH=CH2)]+ (3), while with H2 it gives η6-ethylbenzene complex [Cp*Ir(η6-C6H5CH2CH3)]2+ (4). Complex 1a and 1c react with HCl to give [Cp*Ir(η6-C6H5CH2CH2Cl)]2+ (5a) and [Cp*Ir(η6-C6H5CH(CH3)CH2Cl]2+ (5b), respectively.

Reactions, Hydrogenation and Isomerization of Unsaturated Esters with a Rhodium(I)-Perchlorato Complex

  • Jeong Hyun Mok;Chin Chong Shik
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.468-471
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    • 1986
  • The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

Synthesis and Characterization of Tetranuclear Molybdenum(Ⅵ) Complexes with Butylamidoxime Derivatives (부틸아미드옥심 유도체의 몰리브덴(Ⅵ) 사핵 착물의 합성과 성질)

  • Roh, Soo-Gyun;Oh, Sang Oh
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.552-558
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    • 1995
  • The tetranuclear complexes, $X_2[M_{O4}O_12{R'C(NH_2)NO}_2](X= n-Bu_4N^+$, $R'=(CH_3)_2CH$, $CH_3CH_2CH_2$, $CH_3SCH_2$; $X=(CH_3)_2CHC(=NH_2)NH_2^+$, $R'=(CH_3)_2CH$; $X = CH_3CH_2CH_2C(=NH_2)NH_2^+$, $R'=CH_3_CH_2CH_2$; $X=CH_3SCH_2C(=NH_2)NH_2^+$, $R'=CH_3SCH_2)$ have been synthesized by the reactions of monomeric and polynuclear complexes with isobutyl-, butyl- and thiomethylacetamidoxime. The prepared complexes were identified by elemental analysis, infrared, $^1H$ NMR and $^{13}C$ NMR spectroscopy. The structure of complex ${(CH_3)_2CHC(NH_2)_2}_2[M_{O4}O_{12}{(CH_3)_2CHC(NH_2)NO}_2]$ was determined by X-ray single crystal diffraction. Crystal data are follows: Monoclinic, $P2_{1/c}$, $a=10.168(3){\AA}$, $b=11.768(1){\AA}$, $c=13.557(1){\AA}$, ${\beta}=102.08(1)^{\circ}$, $V=1586.2(5){\AA}^3$, Z=2, final R=0.026 for 2951($F_0>3s(F_0)$). This complex is composed of a planar cyclic $[Mo_4({\mu}-O)_4]$ and two ${\mu}_4$-amidoximate.

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$New η^3-Allyl-Alkenyl- and η^3-Allyl-Alkynyl-Ir-Cp^* Compounds from Reactions of [Cp^*Ir(η^3-CH_2CHCHPh)(NCMe)]^+ with Alkynes$

  • Jin, Jong Sik;Jong, Dae Seong;Kim, Mi Yeok;Lee, Hyeon Gwi
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.739-742
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    • 2001
  • Reactions of [Cp*Ir(η3-CH2CHCHPh)(NCMe)]OTf (1) with HC≡CR (R = H, CH2OH) in the presence of bases, B (B=NEt3, PPh3, AsPh3) produce stable Cp*Ir-η3-allyl-alkenyl compounds [Cp*Ir(η3-CH2CHCHPh)(-CH=CH-+B)]OTf (2) and [Cp*Ir(η3-CH2CHCHPh)(-C(CH2OH)=CH- +PPh3)]OTf (3), respectively in high yields. Cp*Ir-η3-allyl-alkynyl compounds Cp*Ir(η3-CH2CHCHPh(-C≡C-R') (4) and Cp*(η3-CH2CHCHPh)Ir-C≡C-p-C6H4-C≡C-Ir(η3-CH2CHCHPh)Cp* (5) have been prepared from reactions of 1 with HC≡CR'(R' = C6H5, p-C6H4CH3, C3H5, C6H9) and HC≡C-p-C6H4-C≡CH in the presence of NEt3.

Gas Sensing Behaviors of SnO2:Cu Nanostructures for CH4, CH3CH2CH3 Gas (SnO2:Cu 나노 구조물의 CH4, CH3CH2CH3 가스 감응 특성)

  • Lee, Ji-Young;Yu, Yoon-Sic;Yu, Il
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.25 no.12
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    • pp.974-978
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    • 2012
  • The effect of Cu coating on the sensing properties of nano $SnO_2:Cu$ based sensors for the $CH_4$, $CH_3CH_2CH_3$ gas was studied. This work was focussed on investigating the change of sensitivity of nano $SnO_2:Cu$ based sensors for $CH_4$, $CH_3CH_2CH_3$ gas by Cu coating. Nano sized $SnO_2$ powders were prepared by solution reduction method using stannous chloride($SnCl_2{\cdot}2H_2O$), hydrazine($N_2H_2$) and NaOH and subsequent heat treatment. XRD patterns showed that nano $SnO_2$ powders with rutile structure were grown with (110), (101), (211) dominant peak. The particle size of nano $SnO_2:Cu$ powders at 8 wt% Cu was about 50 nm. $SnO_2$ particles were found to contain many pores, according to SEM analysis. The sensitivity of nano $SnO_2:Cu$ based sensors was measured for 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air with that in target gases. The sensitivity for both $CH_4$ and $CH_3CH_2CH_3$ gases was improved by Cu coating on the nano $SnO_2$ surface. The response time and recovery time of the $SnO_2:Cu$ gas sensors for the $CH_4$ and $CH_3CH_2CH_3$ gases were 18~20 seconds, and 13~15 seconds, respectively.

A Comparison of the Leaving Group Ability of Transition Metal Carbonyl Anions vs. Halides : Reaction of $MH^-$ with M'-R $(MH^-\;=\;HW(CO)_4\;-P(OMe)_3\;^-,\;HW(CO)_5\;^-,\;HCr(CO)_5\;^-,\;HFe(CO)_4\;^-;\;M'-R=CpMo(CO)_3(CH_3),\;CpMo(CO)_3{CH_2CH(CH_2)_2})$

  • Yong Kwang Park;Seon Joong Kim;Carlton Ash
    • Bulletin of the Korean Chemical Society
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    • v.11 no.2
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    • pp.109-114
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    • 1990
  • The anionic transition metal hydrides $(HW(CO)_4P(OMe)_3\;^-,\;HW(CO)_5\;^-,\;HCr(CO)_5\;^-,\;HFe(CO)_4\;^-)$ react with transition metal alkyl $(CpMo(CO)_3(CH_3)$ to yield $CH_4\;and\;CH_3CHO$ in addition to the inorganic products $(CpMo(Co)_3\;^-$, etc.). The reaction of these anionic metal hydrides with CpMo(CO)3{CH2CH(CH2)2} may lead to an elucidation of the reaction mechanisms involved; the organic product distributions are among $CH_4,\;CH_2\;=\;CHCH_2CH_3$, and $CH_3CH(CH_2)_2$, depending upon the anionic metal hydride used. These anionic metal hydrides also are reported to undergo a hydride-halide exchange reaction with organic halides; therefore, these similar reactions have been compared in terms of leaving group ability $(CpMo(CO)_3\;^-\;vs.\;Br^-)$ and the mechanistic pathways.

Preparation and Polymerization of Alkenylsilanes (Alkenylsilane의 제조와 고분자화반응)

  • Kim, Chung Kyun;Choi, Soon Kyu;Park, Eun Mi;Jung, In Kyung
    • Journal of the Korean Chemical Society
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    • v.41 no.2
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    • pp.88-97
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    • 1997
  • The silyltriflates$(Ph_{3-n}SiH(OTf)_n)$have been produced by the reaction of triphenylsilane and triflic acid$(CF_3SO_3H)$at low temperature. These highly reactive compounds are a valuable reagent for the synthesis of numerous new functional substituted silane derivatives. The reaction of silyltriflates with alkenyl- and alkynylmagnesium bromide as well as organolithium compounds gave new silanes$Ph_2SiHR(R=\;C(CPh,\;CH=CH_2,\;CH_2CH=CH_2,\; (CH_2)_2CH=CH_2,\;(CH_2)_3CH=CH_2)$in high yields. The hydrosilation of prepared alkenyl- and alkynylsilanesPh_2SiHR$in the presence of a platinum catalyst(Pt/C) at high temperature$(200{\circ}C)$gave carbosilane polymers$((Ph_2SiCH=CPh)_n$and$(Ph_2Si(CH_2)m)n;\;m=2∼4, n{\ge}10)$along with five- and six-membered silaalkane ring compounds derived from intramolecular hydrosilation reactions. All of the prepared compounds are confirmed by NMR, UV, IR and mass spectroscopy as well as elemental analysis.

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Hydrogen-Atom and Charge Transfer Reactions within Acetylene/Methanol and Ethylene/Methanol Heteroclusters

  • 신동남;최창주;정경훈;정광우
    • Bulletin of the Korean Chemical Society
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    • v.17 no.10
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    • pp.939-943
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    • 1996
  • Reactions that proceed within mixed acetylene-methanol and ethylene-methanol cluster ions were studied using an electron-impact time-of-flight mass spectrometer. When acetylene and methanol seeded in helium are expanded and ionized by electron impact, the ion abundance ratio, [CH3OH+]/[CH2OH+] shows a propensity to increase as the acetylene/methanol mixing ratio increases, indicating that the initially ionized acetylene ion transfers its charge to adjacent methanol molecules within the clusters. Investigations on the relative cluster ion intensity distributions of [CH3OH2+]/[CH3OH+] and [(CH3OH)2H+]/[CH3OH·CH2OH+] under various experimental conditions suggest that hydrogen-atom abstraction reaction of acetylene molecule with CH3OH ion is responsible for the effective formation of CH2OH ion. In ethylene/methanol clusters, the intensity ratio of [CH3OH2]/[CH3OH] increases linearly as the relative concentration of methanol decreases. The prominent ion intensities of (CH3OH)mH over (CH3OH)m-1CH2OH ions (m=1, 2, and 3) at all mixing ratios are also interpreted as a consequence of hydrogen atom transfer reaction between C2H4 and CH3OH to produce the protonated methanol cluster ions.

Gas Sensing Characteristics of SnO2 Coated with Catalyst for Hydrocarbon Gas (촉매가 첨가된 SnO2 가스센서의 탄화수소 가스에 대한 감응 특성)

  • Lee, Ji-Young;Yu, Il
    • Korean Journal of Materials Research
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    • v.22 no.7
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    • pp.358-361
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    • 2012
  • Co and Ni as catalysts in $SnO_2$ sensors to improve the sensitivity for $CH_4$ gas and $CH_3CH_2CH_3$ gas were coated by a solution reduction method. $SnO_2$ thick films were prepared by a screen-printing method onto $Al_2O_3$ substrates with an electrode. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a chamber. The structural properties of $SnO_2$ with a rutile structure investigated by XRD showed a (110) dominant $SnO_2$ peak. The particle size of the $SnO_2$:Ni powders with Ni at 6 wt% was about 0.1 ${\mu}m$. The $SnO_2$ particles were found to contain many pores according to a SEM analysis. The sensitivity of $SnO_2$-based sensors was measured for 5 ppm of $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air to that in the target gases. The results showed that the best sensitivity of $SnO_2$:Ni and $SnO_2$:Co sensors for $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature was observed in $SnO_2$:Ni sensors coated with 6 wt% Ni. The $SnO_2$:Ni gas sensors showed good selectivity to $CH_4$ gas. The response time and recovery time of the $SnO_2$:Ni gas sensors for the $CH_4$ and $CH_3CH_2CH_3$ gases were 20 seconds and 9 seconds, respectively.

Studies on the Distribution Coefficient of the Primary, Secondary, Tertiary Amine and Quaternary Ammonium-methylorange Salts

  • Kim, Bak-Kwang
    • YAKHAK HOEJI
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    • v.18 no.3
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    • pp.183-189
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    • 1974
  • Distribution coefficients between nitrobanzene solution and deionized water, show a straight line when the number of alkyl radicals against the logarithm of distribution coefficient of the salts was plotted. After extracting salts of the indicator and the cationic surfactants with organic solvents, and employing the colorimetric method was used. A calculation method of distribution coefficients of the salts in the organic solvent has been suggested and it could be used for the extraction equilibrium of the primary amine, $CH_{3}(CH_2)_{n}NH_3^+$ secondary amine, $CH_{3}(CH_2)_{n}NH_{2}(CH_3)^+$, tertiary amine $CH_{3}(CH_2)_{n}NH(CH_3)_2^+$ and quaternary ammonium, $CH_{3}(CH_2)_{n}N(CH_3)_3^+$MO$^-$salts, (n=3,5,7,11).

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