• Analytical Science and Technology
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• v.11 no.1
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• pp.42-46
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• 1998

The reaction of $({\eta}^5-C_5Me_5)_2K$ with $BiCl_3$ yielded $({\eta}^5-C_5Me_5)_2BiCl$[I], the first organobismuth compound with ${\pi}$-bonded cyclopentadienyl ring. The compound I which was the violet crystal (yield, 30%) was decomposed to $PCpBiCl_2$. The Structure of $({\eta}^5-C_5Me_5)_2BiCl$ was identified as single crystal by X-ray diffraction method. The eliminated product $C_{20}H_{30}$, triclinic crystal of space group p1(Z=2) which was attached with C-C ${\sigma}$-bond of two cyclopentadienyl was defined by the structural analysis.

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2757-2758
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• 2010

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.99.1-99.1
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• 2015

ALD와 CVD 공정을 진행 하는데 있어서 전구체의 평가 및 실시간 분해과정을 확인 하는 것은 매우 중요하다. 본 실험에서는 고유전 산화막에 쓰이는 Cyclopentadienyl Tris (dimethylamino) Zirconium, CpZr(NMe2)3 전구체의 증기압 특성과 FTIR, QMS를 활용하여 $250^{\circ}C$ 온도구간 에서의 분해과정을 실시간으로 측정 하였다. CpZr(NMe2)3의 Atomic mass 는 288 amu이며 증기압은 $60^{\circ}C$에서 0.075 Torr로 측정되었다. 온도가 증가 함에 따라 FTIR 에서 CH3 symmetric stretch (2776 cm-1), CH3 symmetric stretch (2865 cm-1) intensity가 줄어 들게 되었으며 QMS에서도 15 amu (Methyl)의 신호가 온도가 증가함에 따라 감소함을 확인 할수 있었다. QMS에서 Cp의 이온전류가 사라진 이유는 Cp가 모체인 CpZr에서 모두 다 분리되었고 신호가 없어 졌기 때문이다. 본 연구를 통해서 FTIR 단독으로는 얻을수 없는 온도에 따른 세부적인 분해과정을 QMS로 실시간 측정 함으로서 FTIR의 분석 결과와 산호보완 할수 있게 되었다.

• Polymer(Korea)
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• v.30 no.1
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• pp.64-69
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• 2006

A series of dinuclear half-sandwich titanium complexes with aryloxy substituent at titanium$[(\eta^5-cyclopentadienyl)(aryloxy)TiCl_2]_2[(CH_2)_n]$ (n=3, n=6, n=9) have been successfully synthesized and their styrene polymerization properties have been investigated. All complexes are characterized by $^1H\;NMR,\;^{13}C\;NMR$, elemental analysis, and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has beer conducted in the presence of MMAO. It was found that (i) all the prepared complexes were very effective catalyst for the production of SPS (syndiotactic polystyrene), (ii) the complex with the longest bridge between the two active sites exhibited greatest catalytic activity among the three catalysts, but produced SPS with the smallest molecular weight, (iii) the activities of dinuclear half-titanocens with aryloxy substitution at titanium metal were greater than those of the chloride substituted compounds. These results indicate that not only the nature of the bridge between the two active sites but also the property of substituents at the metal exert a significant influence on the polymerization behaviors of the dinuclear half-titanocene.

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.583-592
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• 2003

The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.852-854
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• 2005

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.159-160
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• 2006

We developed novel catalyst, PHENICS composed of the combination of a cyclopentadienyl group to perform a high catalytic activity and a bulky phenoxy group, which performs the production of high molecular weight polyolefin. The polymerization activity of PHENICS at high temperature is higher than well-known CGC catalyst. PHENICS showed the excellent ability of comonomer incorporation into polymer chain. The obtained copolymer had a high molecular weight. The PHENICS catalyst is also active to the copolymerization of ethylene and several vinyl comonomers such as styrene, norbornen, and conjugated dienes. We will discuss new cocatalysts for PHENICS to improve activity and the ability of molecular weight control.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.967-970
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• 2013

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1495-1496
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• 2005

• Journal of the Korean Chemical Society
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• v.42 no.2
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• pp.177-183
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• 1998

By the reactions of a $C_{2}$-chiral ligand, (+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(6) with $[\pi-allyl chloroplatinum(II)]_4$, and $CpCo(CO)_2$ respectively, three new complexes, ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene perchlorate(1), ($\pi$-allyl)platinum(II)(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene chloride(2), ($\eta^5$-cyclopentadienyl)cobalt(I)-(+)-11S,12S-bis[2,2'-(diphenylphosphino)benzanilido]-9,10-dihydro-9,10-ethanoanthracene(3) were prepared. $\eta^3$-Cyclohexenyl)palladium(II)1,2-bis(diphenylphosphino)ethane perchlorate(4) was obtained by the reaction of ($\eta^3$-cyclohexenyl)palladium(II) chloride dimer with a symmetric ligand, 1,2-bis(diphenylphosphino)ethane and lithium perchlorate. These complexes were identified by NMR-, IR-, and Mass-Spectrophotometers and elemental analyzer.