• 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.

• 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.

• Proceedings of the Korea Crystallographic Association Conference
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• 2004.11a
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• pp.14-14
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• 2004

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.549-554
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• 1993

The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

• Journal of the Korean Chemical Society
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• v.41 no.12
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• pp.639-644
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• 1997

Novel carbonylruthenium (Ⅲ) complex Cp*Ru(CO)Cl2(2, Cp*=η5-C5Me5) was synthesized by the reaction of [Cp*RuCl2]2(1) with CO in toluene. The effective magnetic moment (Veff=1.81 B.M.) derived from the magnetic susceptibility measurement of the complex (2) was consistent with the presence of one "single" unpaired electron. Dibromocarbonylruthenium (Ⅲ) complex Cp*Ru(CO)Br2(3) was obtained by the reaction of complex (2) with KBr in toluene. Complex (2) was easily reduced by the reaction with phosphine in toluene to give the corresponding Ru (Ⅱ) complex Cp*Ru(CO)(PR3)Cl (4a∼4e, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3).

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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• pp.413-421
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• 1986

Hydrocarbon solution of $Cp_2Zr(CH_3)Cl$ react rapidly with $Na_2Fe(CO)_4$ (1/2 equiv.) to yield $[Cp_2Zr(CH_3)]_2Fe(CO)_4$ and NaCl. The more soluble metal-metal bonded complex $[Cp_2ZrC_8H_{17}]_2Fe(CO)_2$ has also been prepared through the reaction of $Cp_2Zr(C_8H_{17})BF_4$ and $Na_2Fe(CO)_4 (1/2 equiv.). The complexes were characterized by IR, $^1H$ NMR, ^{13}C$ NMR, and elemental analysis. The infrared spectrum of $[Cp_2ZrR]_2Fe(CO)_4$ shows four bands, which is indicative of a cis-structure. The $^{13}C$ NMR spectrum provides evidence for the cis-structure.

• Proceedings of the Korea Crystallographic Association Conference
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• 2002.11a
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• pp.30-30
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• 2002

Heating [Cp＊Rh(η²-NO₃)(OTf) (1) and PhC≡CPh in EtOH for 3 h gave a η⁴-cyclobutadienerhodium complex, [Cp＊Rh(η⁴-C₄Ph₄)] (2). Complex 1 reacted with HC=CPh in acetone at room temperature for 3 h to give a (η⁴-cyclobutadiene)-rhodium complex, [Cp＊Rh(η⁴-C₄HPhC=CPh)] (3). Whereas, the reactions of 1 with HC=CCH₂Cl in acetone at room temperature for 3 h gave the triply halide-bridged dinuclear rhodium complex, [Cp＊Rh(μ₂-Cl)₃RhCp＊](OTf) (4). Complexes 2-4 have been structurally characterized by X-ray diffraction.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.669-673
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• 1993

The CO substitution reactions of the complex, $Cp(S-2,4-Me_2C_5H_5)CrCo$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline were ${\Delta}H^{\neq}\;=\;22.0\;kcal{\cdot}mol^{-1}$, ${\Delta}S^{\neq}=\;-3.8cal{\cdot}mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S{\neq}$ suggests an ${\eta}^5-S{\to}{\eta}^5-U$ conversion of the pentadienyl ligand. This suggestion was confirmed by the Extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy of $Cp(S-2,4-Me_2C_5H_5$)CrCO is about 0.42 kcal/mol more lower than that of $Cp(U-2,4-Me_2C_5H_5)CrCO$ and the energy of $[Cp(U-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq} $ transition state is about 2.43 kcal/mol lower than that of $[Cp(S-2,4-Me_2C_5H_5)Cr{\cdots}CO]^{\neq}$ transition state.

• Journal of Korea Foundry Society
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• v.13 no.4
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• pp.350-358
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• 1993

Aluminum base composites reinforced with various amount of SiC particles and Mg contents have been investigated by different fabrication method for twenty-years. In this paper, how the decomposition and dissolution behaviors of $SiCp(20{\mu}m)$ in the melt of Al composites arised was studied. As the results, the decomposition and dissolution of SiCp into the melt of Al composites increased with increase of the temperature above $720^{\circ}C$, and holding time at a given melting temperature. Because SiC is thermodynamically unstable in this Al-SiCp composite at temperature above the liquidus, SiCp dissolves and reacts with Al in matrix to form $Al_4C_3$ according to following chemical equation $4Al+3SiC{\rightarrow}Al_4C_3+3Si$, Si decomposed and dissolved from SiCp increases Si content of matrix, while liquidus temperature of matrix decrease with increase of SiC content in matrix. The hardness of SiCp decreased with increase of the melting temperature, the hardness of the matrix /particle interface increased with increase of the melting temperature due to increase of the $Mg_2Si$ and $Al_4C_3$ intermetallic compounds, etc.

• Journal of Integrative Natural Science
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• v.6 no.1
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• pp.34-38
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• 2013

Tributyltin hydride ($n-Bu_3SnH$), an endocrine disruptor, was slowly polymerized by the group 4 ${Cp^{\prime}}_2TiCl_2/N$-selectride (Cp' = $C_5H_5$, Cp; $Me-C_5H_4$, Me-Cp; $Me_5C_5$, $Cp^*$) catalyst combination to give two phases of products: one is an insoluble cross-linked solid, polystannane in 3-25% yield as minor product via disproportionation/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 65-90% yield as major product via simple dehydrocoupling process. Disproportionation/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane. The disproportionation/dehydrocoupling of a tertiary hydrostannane mediated by early transition metallocene/inorganic hydride is quite unusual and applicable.