• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1065-1067
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• 2004

• Journal of the Korean Chemical Society
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• v.47 no.6
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• pp.585-590
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• 2003

Cobalt oxygen carrier complex N,N'-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen) was prepared at $25{\circ}C$. UV and visible absorption spectra of the complex and hydrazobenzene were studied in non-aqueous solvent methanol in the range of wavelength 200-600 nm. The oxidation of hydrazobenzene by oxygen in non-aqueous solvent is catalysed by Co(3MeOsalen). In the presence of triphenylphosphine($PPh_3$), the rate decreases in methanol. This is presumably attributable to the coordination of $PPh_3$ to the Co(3MeOsalen), resulting in the catallytically inactive compound. The initial rates of the oxidation of hydrazobenzene with the ligand triphenylphosphine were measured by the theoretical values of the rates, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$. This fact would be a poorer σ-donor ligand than methanol.

• Bulletin of the Korean Chemical Society
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• v.18 no.10
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• pp.1061-1066
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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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• v.18 no.10
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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.

• Korean Journal of Crystallography
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• v.6 no.2
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• pp.93-97
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• 1995

Re(≡NC6H5)(PPh3)2CI3, I, reacted with, 1,2-bis(diphenylphosphino)ethane (DPPE) to give fac-Re(≡NC6H5)(DPPE)CI3, II. The product has been characterized by 1H-NMR, elemental analysis, and X-ray crystallography. II Crystalizes in the monoclinic space group Pc, with cell parameters a=11.083(3)Å, b=10.930(1)Å, c=14.081(2)Å, β=108.37(2)°, Z=2. Least-squares refinement of the structure led to a R(wR2)factor of 0.0254(0.0607) for 2888 unique reflections of I>2σ(I) and for 352 variables.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.849-852
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• 1994

The ${\alpha},{\beta}$-enoyl chiral iron complexes, ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)(PPh_3)$ (1) were prepared from ${\alpha},{\beta}-enoyl-{\eta}^5-(C_5H_5)Fe(CO)_2$(2) and triphenylphosphine through a photochemical ligand substitution followed by carbonylation.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.150-153
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• 1994

By treating mer, trans-Re(${\equiv}NC_6H_5)(PPh_3)_2Cl_3$, Ⅰ, with 5 atm of CO at room temperature for 52 h, fac-Re(${\equiv}NC_6H_5)(CO)(PPh_3)Cl_3$, Ⅱ, was obtained as dark green precipitates in 81% yield. The crystal structure of Ⅱ was determined through X-ray diffraction. Ⅱ crystallizes in the monoclinic system, space group $P2_1/n$ with cell parameters a=9.740 (2) ${\AA}$, b=16.210 (5) ${\AA}$, c=16.192 (6) ${\AA}$, ${\beta}$=97.50 $(2)^{\circ}$, and Z=4. Least-squares refinement of the structure led to a R$(R_w)$ factor of 0.030 (0.036) for 2878 unique reflections of I>3${\sigma}(I)$ and for 241 variables. In comparison to the starting material Ⅰ, the bond distance of Re-N became longer from 1.726 (6) to 1.736 (5) ${\AA}$ and the bond angle of Re-N-C(Ph) became smaller from 172.6 (6) to 167.0 $(2)^{\circ}$, indicating that the Re-N bond in Ⅱ is weakened and has a less triple-bond character than that in Ⅰ.

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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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.

• Proceedings of the Korea Crystallographic Association Conference
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• 2000.11a
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• pp.13-13
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• 2000

• Bulletin of the Korean Chemical Society
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• v.16 no.12
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• pp.1237-1239
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• 1995