• Bulletin of the Korean Chemical Society
• /
• v.10 no.4
• /
• pp.360-362
• /
• 1989

Catalytic isomerization of unsaturated alcohols to the corresponding carbonyl compounds with$Rh(ClO_4)(CO)(PPh_3)_2\;(1)\;and\;[Rh(CO)(PPh_3)_3]ClO_4$ (2) is faster under hydrogen (where hydrogenation also occurs to give saturated alcohols) than under nitrogen. The isomerization under hydrogen seems to occur through an alkylhydridorhodium(III) complex which also undergoes reductive elimination to give hydrogenation products, saturated alcohols. The isomerization under hydrogen is faster with 2 than with 1, which is understood by acceleration of the last step, enol formation by $PPh_3$ dissociated from 2 and present in the reaction mixture when 2 is used as catalyst. Relative rates of the isomerization observed for different unsaturated alcohols are interpreted by steric effects of substituted groups and numbers of hydrogens to be abstracted by the rhodium of the intermediate, alkylhydridorhodium(III) to undergo the reductive elimination to give enol which is then rapidly converted into a carbonyl compound. It has been observed that the hydrogenation is relatively significant when reactions occur slowly whereas the isomerization is predominant when reactions proceed rapidly.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.6
• /
• pp.466-468
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.6
• /
• pp.468-471
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.11
• /
• pp.1682-1688
• /
• 2005

Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.

• Journal of the Korean Chemical Society
• /
• v.32 no.5
• /
• pp.501-506
• /
• 1988

The effects of alkali promoters on the activity and selectivity of Co/NaY catalyst have been investigated. The catalysts were prepared by impregnating NaY with aqueous solutions of alkali compounds and a benzene solution of $Co_2(CO)_8$. Hydrocarbon synthesis was studied in a flow reactor under the reaction conditions : temperature = 200∼250$^{\circ}C$, space velocity = 120∼$160hr^{-1}$, pressure = 1 atm, $H_2$/CO = 1. As the basicity of alkali promoter increases, the olefin selectivity, probability of chain growth, and CO$_2$ formation increase and methane formation decreases. The activity of CO hydrogenation increases with the pH of alkali solutions.

• Applied Chemistry for Engineering
• /
• v.28 no.3
• /
• pp.326-331
• /
• 2017

Castor oil can be used as a useful raw material for chemical industries such as intermediates of surfactants through hydrogenation reaction. In this study, effects of the preparation method and pretreatment condition on the nickel catalyst for the hydrogenation of castor oil were investigated. The nickel catalyst was supported on the silica carrier by the precipitation method with different Ni contents, solution pH values, and precipitants. Repeated pretreatments of oxidation and reduction cycles were then carried out. The activity of the nickel catalyst was measured by comparing the iodine value of the castor oil. The dispersion of nickel on the catalyst was analyzed by X-ray diffraction (XRD), $N_2$ adsorption-desorption, and transmission electron microscopy (TEM). The activity of nickel catalyst was also compared by CO oxidation experiments. The redispersion of nickel occurred on the silica by repeated oxidation and reduction cycles, and this effect contributed to promoting the castor oil hydrogenation activity.

• Journal of Magnetics
• /
• v.8 no.3
• /
• pp.124-127
• /
• 2003

HDDR (hydrogenation, disproportionation, desorption, recombination) and mechanical milling processes have been applied to the $SmCo_{5}$ alloy in an attempt to produce a highly coercive powder. The $SmCo_{5}$ alloy had very high structural stability under the hydrogen atmosphere and the 1:5 phase was only partially disproportionated under up to 10 kgf/$\textrm{cm}^2$ hydrogen gas. The partially disproportionated material was recombined not into 1:5 phase after the HDDR, but rather into multi-phase mixture consisting of 1:5, 2:17, 2:7 and 1:7 phases. The $SmCo_{5}$ alloy HDDR-treated with hydrogen up to 10 kgf/$\textrm{cm}^2$ had poor coercivity. For a useful HDDR to prepare a high coercivity $SmCo_{5}$ alloy powder, much higher hydrogen pressure well exceeding 10 kgf/$\textrm{cm}^2$ would be required. The $SmCo_{5}$ alloy lump was amorphized by an intensive mechanical milling, and it was crystallised ultra-finely by a subsequent optimum annealing. The optimally annealed material had very high coercivity, and it was found that the mechanical milling followed by an annealing was an effective way of producing highly coercive $SmCo_{5}$ alloy powder.

• Bulletin of the Korean Chemical Society
• /
• v.8 no.3
• /
• pp.185-189
• /
• 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 $100^{\circ}C$.

• Journal of the Korean Ceramic Society
• /
• v.36 no.5
• /
• pp.504-512
• /
• 1999

The high-quality carbon nanofibers were prepared by chemical vapor deposition of gas mixtures of CO-H2 and C3H8-H2 over Fe-Cu and Ni-Cu bimetallic catalysts. The yield and structure of carbon nanofiber produced were altered by the change of catalyst composition and reaction temperature. The high yields were obtained around 500$^{\circ}C$ with e-Cu catalyst and around 700-750$^{\circ}C$ with Ni-Cu catalyst and the relatively higher yields were obtained with the bimetallic catalyst containing 50-90% of Ni and Fe respectively in comparison with the pure metals. The carbon nanofibers produced over the Fe-Cu catalyst at around 500$^{\circ}C$ with the maximum yields had the highest surface ares of 160-200 m2/g around 650$^{\circ}C$ which was slightly lower than the temperature for maximum yields. In order to examine the characteristics of carbon nanofibers as catalyst support Ni and Co metals were supporte on the carbon nanofibers and CO hydrogenation reaction was performed with the catalysts. The particle size distribution of Ni and Co supported over the carbon nanofibers were 6-15 nm and the CO hydrogenation reaction rate with the carbon-nanofiber supported catalysts was much higher than that over the other supports.

• Journal of the Korean Chemical Society
• /
• v.40 no.6
• /
• pp.445-452
• /
• 1996

Catalytic hydrogenation of ketones and aldehydes by RuH(NO)$L_3$ ($L_3$: $PPh_3$, PhP($CH_2CH_2PPh_2$)$_2$(etp)) was investigated to examine the reaction mechanism and the competence of hydridonitrosyl complexes as catalysts for organic synthesis. RuH(NO)$L_3$ showed catalytic activity for the hydrogenation and the activities of catalysts were dependent on the steric and electronic factors. The less the steric demands of the substrates become, the more activity the catalysts show. For the electronic effect, the more the partial positive charge on the carbonyl carbon atom in ketones becomes and the more the double bond character of carbonyl group in aldehydes becomes, the more active the catalysts are. These results reflect the difference of reaction mechanisms of two substrates, ketones and aldehydes. Catalytic activities of RuH(NO)(etp) and RuH(NO)($PPh_3$)$_3$ in the presence of extra $PPh_3$ toward hydrogenation showed the existence of a reaction pathway accompanied with the change of the bonding modes of NO ligand. The roles of excess $PPh_3$ change with increase of the mole ratio of $PPh_3$ to catalysts; prevention of ligand dissociation from comlexes → bases → ligands. The activity of RuH(NO)(etp) was lower than that of RuH(NO)($PPh_3$)$_3$ toward the hydrogenation of the same substrates mainly due to the structural difference. These catalysts showed the selectivity toward olefin hydrogenation over carbonyl groups in the competitive reaction.