• Bulletin of the Korean Chemical Society
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• 제18권10호
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• pp.1050-1052
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• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.372-376
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• 1987

Acetone solution of quinoline-8-carbaldehyde reacts with $[Rh(cod)(PPh_3)_2] PF_6$and $[Ir(cod)(PPh_3)_2] PF_6$ to yield $[Rh(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (1) and $[Ir(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (2), respectively. The compound $[Ir(cod)(PPh_3)_2] PF_6$ also reacts with $Ph_2PC_6H_4-o-CHO$ in the acetone / $H_2O$ mixture to give $[Ir(Ph_2PC_6H_4-o-CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (3). Compounds 1, 2, and 3 were characterized by infrared, $^1H$ NMR, $^{31}P$ NMR spectra and conductivity measurement. The $^1H$ NMR spectra of 1, 2, and 3 support the presence of a terminal hydride that is cis to the phosphine. The IR band of 3 at 2185 $cm^{-1}$, which is assigned to $\nu$(Ir-H), and the hydride cleavage reaction of 3 with $CCl_4$, provide evidence for the Ir-H bond.

• Bulletin of the Korean Chemical Society
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• 제16권6호
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• pp.524-528
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• 1995

The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

• 대한화학회지
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• 제41권12호
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• pp.639-644
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• 1997

톨루엔 용매중에서 Cp*Ru(CO)Cl2(2, Cp*=η5-C5Me5)과 CO를 반응시켜 상자기성의 3가 카르보닐루테늄착물 [Cp*Ru(CO)Cl2](2)를 합성하였다. 자기화율의 측정으로부터 얻어진 착물(2)의 유효자기모멘트 값은 1.81 B. M.으로 이는 분자내 짝을 이루지 않는 전자가 1개 있는 경우와 거의 일치하였다. 착물(2)는 톨루엔 용매중에서 KBr과의 반응에 의해 3가의 디브로모루테늄착물 Cp*Ru(CO)Br2(3)으로 변환되었고, 톨루엔 용매중에서 포스핀과의 반응에 의해서는 반자기성인 2가 루테늄착물 Cp*Ru(CO)(PR3)Cl (4a∼4e, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3)로 쉽게 환원되었다.

• Safety and Health at Work
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• 제2권1호
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• pp.39-51
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• 2011

Objectives: This study was designed to evaluate exposure levels of various chemicals used in wafer fabrication product lines in the semiconductor industry where work-related leukemia has occurred. Methods: The research focused on 9 representative wafer fabrication bays among a total of 25 bays in a semiconductor product line. We monitored the chemical substances categorized as human carcinogens with respect to leukemia as well as harmful chemicals used in the bays and substances with hematologic and reproductive toxicities to evaluate the overall health effect for semiconductor industry workers. With respect to monitoring, active and passive sampling techniques were introduced. Eight-hour long-term and 15-minute short-term sampling was conducted for the area as well as on personal samples. Results: The results of the measurements for each substance showed that benzene, toluene, xylene, n-butyl acetate, 2-methoxy-ethanol, 2-heptanone, ethylene glycol, sulfuric acid, and phosphoric acid were non-detectable (ND) in all samples. Arsine was either "ND" or it existed only in trace form in the bay air. The maximum exposure concentration of fluorides was approximately 0.17% of the Korea occupational exposure limits, with hydrofluoric acid at about 0.2%, hydrochloric acid 0.06%, nitric acid 0.05%, isopropyl alcohol 0.4%, and phosphine at about 2%. The maximum exposure concentration of propylene glycol monomethyl ether acetate (PGMEA) was 0.0870 ppm, representing only 0.1% or less than the American Industrial Hygiene Association recommended standard (100 ppm). Conclusion: Benzene, a known human carcinogen for leukemia, and arsine, a hematologic toxin, were not detected in wafer fabrication sites in this study. Among reproductive toxic substances, n-butyl acetate was not detected, but fluorides and PGMEA existed in small amounts in the air. This investigation was focused on the air-borne chemical concentrations only in regular working conditions. Unconditional exposures during spills and/or maintenance tasks and by-product chemicals were not included. Supplementary studies might be required.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1359-1365
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• 2005

A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

• 공업화학
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• 제8권4호
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• pp.679-684
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• 1997

석유화학공업에서 사용된 유동접촉분해(FCC) 폐촉매의 주성분은 Si와 Al이며, 그외에 Fe, Zn, Ti 등의 기본금속과 알칼리금속 및 Ce, Nd, Ni, V 등의 희유금속이 함유되어 있다. $0.25mo1/dm^3-H_2SO_4$를 침출제로 폐촉매를 침출하였을 때 Ce가 640, Nd가 310, 그리고 V가 $450mg/dm^3$ 함유된 pH 1.0의 침출액을 얻었고, 아미노인산형 킬레이트수지에 의하여 Ce와 Nd를 선택흡착시킨 후, $4.0mol/dm^3-HCl$로 용리시켜 $1.2g/dm^3$의 Ce와 $0.75 g/dm^3$의 Nd 농축액을 얻었다. 농축액을 다시 옥살산 침전 및 공기산화법으로 처리하여 Ce와 Nd의 분리가 가능하였으며, 염소이온 공존하에 추출제 TOPO를 이용한 용매추출법으로 V와 Al을 각각 분리시켜, FCC 폐촉매로부터 순도가 99%인 Ce, Nd 및 V의 분리정제가 가능하였다.

• 대한화학회지
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• 제33권6호
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• pp.657-661
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• 1989

팔라듐 촉매를 이용한 vinylmercuric chlorides의 CO 첨가반응과 커플링반응을 동시에 진행시키는 CO 첨가 호모커플링반응을 실시하여 대칭 디비닐케톤 또는 디비닐 ${\alpha}$-디케톤을 비교적 좋은 수득율로 얻었다. 디비닐케톤과 디비닐 ${\alpha}$-디케톤의 최적 합성조건을 규명하기 위하여 여러가지 vinylmercuric chlorides의 대표적인 모델로서 (E)-styrylmercuric chloride를 선택하여 촉매의 종류 및 그의 양, 염기, 용매 및 반응온도 등의 조건에 따른 수득율의 변화를 조사하였다. 촉매로 10mol%의 dichlorobis(triphenylphosphine)palladium(II), 염기로 등몰의 Pyridine, 10mol%의 요오드 및 10기압의 일산화탄소 존재하에, acetonitrile 용매 중 50${\circ}$C에서 반응시켜 가장 좋은 수득율로 디비닐 ${\alpha}$-디케톤이 얻어졌으며, 상압의 일산화탄소와의 반응에서는 낮은 수득율로 디비닐 ${\alpha}$-디케톤을 얻었다.

• 한국분말재료학회지
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• 제22권6호
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• pp.385-390
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• 2015

We report a synthesis of non-toxic InP nanocrystals using non-pyrolytic precursors instead of pyrolytic and unstable tris(trimethylsilyl)phosphine, a popular precursor for synthesis of InP nanocrystals. In this study, InP nanocrystals are successfully synthesized using hexaethyl phosphorous triamide (HPT) and the synthesized InP nanocrystals showed a broad and weak photoluminescence (PL) spectrum. As synthesized InP nanocrystals are subjected to further surface modification process to enhance their stability and photoluminescence. Surface modification of InP nanocrystals is done at $230^{\circ}C$ using 1-dodecanethiol, zinc acetate and fatty acid as sources of ZnS shell. After surface modification, the synthesized InP/ZnS nanocrystals show intense PL spectra centered at the emission wavelength 612 nm through 633 nm. The synthesized InP/ZnS core/shell structure is confirmed with X-ray diffraction (XRD) and Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES). After surface modification, InP/ZnS nanocrystals having narrow particle size distribution are observed by Field Emission Transmission Electron Microscope (FE-TEM). In contrast to uncapped InP nanocrystals, InP/ZnS nanocrystals treated with a newly developed surface modified procedure show highly enhanced PL spectra with quantum yield of 47%.

• 대한화학회지
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• 제36권1호
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• pp.44-50
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• 1992

착물들의 자기성과 스펙트라의 성질은 d 궤도 함수의 퇴화에 대한 분열과 자외선 가시 분광학적 방법으로 비수용액 속에서 조사하였다. 10Dq의 에너지 크기는 착물들의 스펙트라와 결합에너지 그리고 스핀상태로부터 얻어졌다. 전기화학적 거동은 순환전압 전류법에 의해 측정하였다. 이들의 환원 피크는 Ag/AgCl 전극으로 20mV/s에서 $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$는 $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$이고, 그리고 $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$에서는 $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$로 일전자 비가역적인 과정이었다. 그러나 $Ni^{2+}$ 착물에서는 환원성으로 되지 않았다.