• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.179-183
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• 1987

Reactions of $Rh(ClO_4)(CO)(AsPh_3)_2$ with unsaturated nitriles and aldehyde, L, produce a series of new cationic rhodium (I) complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ (L = $CH_2$ = CHCN, $CH_2$ = C($CH_3$)CN, trans-$CH_3CH$ = CHCN, $CH_2$ = CH$CH_2$CN, trans-$C_6H_5CH$ = CHCN, and trans-$C_6H_5CH$ = CHCHD) where L are coordinated through the nitrogen and oxygen, respectively but not through the ${\pi}$-system of the olefinic group. Dissociation constants for the reaction, $[RhL(CO)(AsPh_3)_2]ClO_4$ $\rightleftharpoons$ $Rh(ClO_4)(CO)(AsPh_3)_2$ + L, have been measured to be $1.20{\times}10^{-4}$ M (L = $CH_2$ = CHCN), $1.05{\times}10^{-4}$ M (L = $CH_2$ = C($CH_3$)CN, $3.26{\times}10^{-5}$ M (L = trans-$CH_3$CH = CHCN) and $6.45{\times}10^{-5}$ M (L = $CH_2$ = CH$CH_2$CN) in chlorobenzene at $25^{\circ}C, and higher than those of triphenylphosphine complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ where L are the corresponding nitriles that are coordinated through the nitrogen atom. The differences in dissociation constants seem to be predominantly due to the differences in ${\Delta}H$ (not due to the differences in ${\Delta}S$). The weaker Rh-N (unsaturated nitriles) bonding in $AsPh_3$ complexes than in $PPh_3$ complexes (based on ${\Delta}H$ values) suggests that the unsaturated nitriles in 2∼5 are good ${\sigma}$-donor and poor ${\pi}$-acceptor.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1781-1786
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• 2007

Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.535-538
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• 1999

Five coordinated water-soluble iridium(l) complex, IrH(CO)(TPPTS)3 (1) (TPPTS = P(m-C6H4SO3Na)3-xH2O) has been prepared from the reaction of IrCl3·3H2O with TPPTS and HCHO in H2O/EtOH solution. Complex 1 catalyzes the hydration of nitrites (RC ≡ N, R = CH3, CICH2, CH3(CH2)4, Ph) in aqueous solution to give the corresponding amides (RCONH2) at 100℃. The hydration of unsaturated nitrites (R'C ≡ N, R'=CH3CH=CH, CH3OCH=CH, trans-PhCH=CH, CH2=C(CH3)) takes place regioselectively on-C ≡ N group to give unsaturated amides (R'CONH2) leaving the olefinic group intact. The yields of the amides seem to be depending on the electrophilicity of the carbon of nitrile: The more the electron withdrawing ability of the substituents on nitrites, the more amides are obtained. The hydration of dinitriles (NC-R-CN, R=(CH2)4, (CH2)6) with complex 1 initially gives mono-hydration products (NC-R-CONH2) which are slowly hydrated further to give dihydration products (H2NCO-R-CONH2). The hydration of 1,4-dicyanobutane has been found to be somewhat faster than that of 1,6-dicyanohexane.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.185-189
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• 1987

Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.

• 대한기계학회:학술대회논문집
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• 대한기계학회 2004년도 추계학술대회
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• pp.1128-1133
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• 2004

A comprehensive experimental and numerical study has been conducted to understand the influence of $CH_{3}Cl$ addition on $CH_{4}/O_{2}/N_{2}$ premixed flames under the oxygen enrichment. The laminar flame speeds of $CH_{4}/CH_{3}Cl/O_{2}/N_{2}$ premixed flames at room temperature and atmospheric pressure are experimentally measured using Bunsen nozzle flame technique, varying the amount of $CH_{3}Cl$ in the fuel, the equivalence ratio of the unburned mixture, and the level of the oxygen enrichment. The flame speeds predicted by a detailed chemical kinetic mechanism employed are found to be in excellent agreement with those deduced from experiments. As $CH_{3}Cl$ addition is increased temperature at the postflame is not almost varied but the heat release rate and $EI_{NO}$ are decreased. The function of $CH_{3}Cl$ as inhibitor on hydrocarbon flames becomes weakened as the level of the oxygen enrichment is increased from 0.21 to 0.5.

• 약학회지
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• 제18권3호
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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).

• Bulletin of the Korean Chemical Society
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• 제7권6호
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• pp.466-468
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• 1986

Reaction of $Ir(ClO_4)(CO)(PPh_3)_2$ with trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ produces a new cationic iridium(I) complex, [Ir (trans-$C_6H_5CH$ = $CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ where trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ seems to be coordinated through the carbonyl oxygen rather than through the $\pi$-system of the olefinic group according to the spectral data. It has been found that Ir$(ClO_4)(CO)(PPh_3)_2$ catalyzes the hydrogenation of $CH_2$ = $CHCO_2C_2H_5$, trans-$CH_3CH$ = $CHCO_2C_2H_5$ and trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ to $CH_3CH_2CO_2C_2H_5$, $CH_3CH_2CH_2CO_2C_2H_5$ and $C_6H_5CH_2CH_2CO_2C_2H_5$, respectively at room temperature under the atmospheric pressure of hydrogen. The relative rates of the hydrogenation of the unsaturated esters are mostly understood in terms of steric reasons.

• 대한기계학회논문집B
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• 제29권2호
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• pp.255-262
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• 2005

A comprehensive experimental and numerical study has been conducted to understand the influence of $CH_{3}Cl$ addition on $CH_4/O_2/N_2$ premixed flames under the oxygen enrichment. The laminar flame speeds of $CH_4/CH_{3}Cl/O_2/N_2$ premixed flames at room temperature and atmospheric pressure are experimentally measured using Bunsen nozzle flame technique, varying the amount of $CH_{3}Cl$ in the fuel, the equivalence ratio of the unburned mixture, and the level of the oxygen enrichment. The flame speeds predicted by a detailed chemical kinetic mechanism employed are found to be in excellent agreement with those deduced from experiments. Even though the molar amount of $CH_{3}Cl$ in a methane flame is increased, temperature at the postflame is not significantly varied, but the calculated heat release rate and emission index of NO are largely decreased for the oxygen enhanced flame. The function of $CH_{3}Cl$ as inhibitor on hydrocarbon flames becomes weakened as the level of the oxygen enrichment is increased from 0.21 to 0.5.

• Nuclear Engineering and Technology
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• 제9권1호
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• pp.39-44
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• 1977

N-methyl-C-phenylalkyl ketimine 이성질체, Ph-CR=N$CH_3$ (R=H, $CH_3$, $CH_3$CH$_2$)의 배치와 형태를 EHT 분자궤도함수법으로 연구하였다. 계산결과는 C=N 이중결함에 대하여 E-형의 배치가 Z-형의 배치보다 안전함을 나타내고 있다. N-methyl-C-phenylaldimine과 N-methyl-C-phenylmethylketimine에서는 phenyl 고러 회전자가 C=N 평면과 동일평면에 있는 형태가 안정하다. N-methyl-C-phenylethylketimine에서는 phenyl 고리와 C=N결합이 동일평면에 있고 회전자 $CH_3$CH$_2$-가 C=N 평면과 90$^{\circ}$인 gauche형이 가장 안정하다.

• 청정기술
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• 제16권3호
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• pp.198-205
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• 2010

염화탄화수소 열분해와 생성물분포 특성을 고찰하기 위해 등온 관형 반응기를 이용해 두 가지 실험을 수행하였다. 첫 번째는 반응분위기에 따른 열분해 특성을 파악하기 위해 $H_2$ 또는 Ar 반응분위기에서 dichloromethane ($CH_2Cl_2$) 분해율과 생성물분포 특성을 고찰하였다. Ar 반응분위기($CH_2Cl_2$/Ar 반응계)에서 보다 $H_2$ 반응분위기($CH_2Cl_2/H_2$ 반응계)에서 $CH_2Cl_2$ 분해율이 더 높았다. 이는 반응성 기체인 $H_2$ 분위기에서 $CH_2Cl_2$ 분해를 촉진시키며 수소 첨가 탈염소반응을 통해 탈염소화된 탄화수소화합물을 생성시키며, 다환방향족탄화수소 (polycyclic aromatic hydrocarbon: PAH)와 soot 생성을 억제하기 때문이다. $CH_2Cl_2/H_2$ 반응계에서 주요생성물로 탈염소화합물인 $CH_3Cl,\;CH_4,\;C_2H_6,\;C_2H_4,\;HCl$ 등이 생성되었으며, 미량 생성물로 chloroethylene이 검출되었다. $CH_2Cl_2$/Ar 반응계에서는 탄소물질수지가 낮았으며 특히 반응온도 $750^{\circ}C$ 이상에서 탄소물질 수지가 더 낮게 나타났다. 주요 생성물로는 chloroethylene과 HCl이 검출되었으며, 미량 생성물로는 $CH_3Cl$과 $C_2H_2$이 검출되었다. 고온 Ar 반응분위기에서 $CH_4$ 주입에 따른 chloroform($CHCl_3$) 분해와 생성물분포 특성을 비교 고찰하였다. $CHCl_3$ 분해율을 비교해 보면 $CH_4$을 주입할 경우($CHCl_3/CH_4/Ar$ 반응계)가 $CH_4$을 주입하지 않았을 경우($CHCl_3$/Ar 반응계)보다 분해율이 낮았다. 이는 $CHCl_3$가 분해되면서 생성되는 활성도가 큰 이중라디칼(diradical)인 :$CCl_2$가 첨가물로 주입된 $CH_4$와 반응하여 소모됨으로써 $CHCl_3$ 분해율이 상대적으로 감소되기 때문이다. Ar 반응분위기에서 $CH_4$ 첨가 여부에 따라 $CHCl_3$이 분해되면서 생성되는 생성물 분포는 큰 차이를 나타내고 있었다. 앞에서 고찰된 각 반응계에서 분해율 비교와 생성물 분포특성을 고려하고 열화학이론 및 반응속도론을 기초로 주요 반응경로를 제시하였다.