• Polymer(Korea)
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• v.35 no.6
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• pp.505-512
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• 2011

Effects of structural features of 4 dinuclear constrained geometry catalysts having paraxylene derivative bridge (DCGC) on copolymerization of ethylene and 1-hexene were investigated. The bridges of three catalysts have para-xylene backbone with a different substituent at benzene ring. The substituents were hydrogen (Catalyst 1), isopropyl (Catalyst 2), n-hexyl (Catalyst 3) and 1-octyl (Catalyst 4). It was found that Catalyst 1 having hydrogen as a substituent exhibited the greatest activity among the four dinuclear CGCs. On the other hand, Catalyst 2 containing isopropyl as a substituent showed the smallest activity. Very interestingly, Catalyst 2 was able to produce about 6 times higher molecular weight polymer than Catalyst 3 and 4. Catalyst 3 and 4 having a long alkyl chain substituent revealed the biggest comonomer response to generate polyethylene copolymer containing more than 40% 1-hexene contents. These results suggest that the control of the substituent of para-xylene bridge of dinuclear CGC can provide a proper method to adjust the microstructure of polyethylene copolymers.

• Proceedings of the Korea Crystallographic Association Conference
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• 2003.11a
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• pp.16-16
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• 2003

• Bulletin of the Korean Chemical Society
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• v.20 no.4
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• pp.491-493
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• 1999

• Bulletin of the Korean Chemical Society
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• v.20 no.9
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• pp.1105-1107
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• 1999

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3973-3978
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• 2011

The reductive pinacol coupling reaction of aldehydes or ketones creating a new C-C bond has been a major tool to produce 1,2-diol compounds. The reaction mechanism is known to be composed of sequential three steps (activation, coupling, and dissociation). In this work, we studied the dissociation step of half-titanocene-based catalytic systems. Cp and $Cp^*$ derivatives of the pinacolato-bridged dinuclear complex were synthesized and evaluated as possible models for intermediates from the coupling step. We monitored $^1H$-NMR spectra of the reaction between the metalla-pinacol intermediates and $D_2O$. New reaction routes of the dissociation step including oxo- and pinacolato-dibridged dinuclear complexes and oxo-bridged multinuclear complexes have been suggested.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.224-225
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• 2006

The Ethylene polymerization behavior of a series of polymethylene bridged dinuclear CGC $[Zr({\eta}^{5}:{\eta}^{1}-C_{9}H_{5}SiMe_{2}NCMe_{3})Me_{2}]_{2}[(CH_{2})_{n}]\;[_{n}=6(1),\;9(2),\;12(3)]$ in the cocatalytic activation with $Ph_{3}C^{+}B^{-}(C_{6}F_{5})_{4}\;(B_{1})\;or\;Ph_{3}C^{+}(C_{6}F_{5})_{3}B^{-}C_{6}F_{4}B^{-}(C_{6}F_{5})_{3}Ph_{3}C^{+}\;(B_{2})\;or\;B(C_{6}F_{5})_{3}\;(B_{3})$ were investigated to study the nuclearity effects as well as the counteranion effects. The ethylene polymerization and ethylene/1-hexene copolymerization were conducted at $30^{\circ}C$ It was found that both in ethylene polymerization and ethylene/1-hexene copolymerization, activities increased in the order of 1 < 2 < 3, which indicates the presence of longer bridge between two active sites contributes more efficiently to facilitate the polymerization activity.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2617-2622
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• 2011

Two new Zn(II) complexes, $[Zn_2(dpa)_2(phen)_2(H_2O)_2]{\cdot}H_2O$ (1) (dpa = dephenate, phen = 1,10-phenanthroline) and [$Zn_2(dpa)_2(bpy)_2(H_2O)_2$] (2) (bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear zinc(II) complexes bridged by dpa dianions, respectively. The zinc ions in 1 exhibit a distorted square pyramidal environments, while the zinc ions in 2 exhibit a trigonal bipyramid geometry. In each complex, the dpa ligand is coordinated to zinc ions as a bis-monodentate.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.573-576
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• 2006

• Korean Journal of Crystallography
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• v.17 no.2
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• pp.46-50
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• 2006

The dinuclear copper(II) complex {[Cu(pmea)Cl][Cu$(H_2O)_3]}Cl_2{\cdot} H_2O$ (1) (Hpmea=bis(2-pyridvlmethyl)amino-2-ethanoic acid) has been synthesized and characterized. It crystallizes in the monoclinic system $P2_1/c$, a=9.0008(6) ${\AA}$, b=28.0171(19) ${\AA}$, c=8.5590(6) ${\AA}$, $\beta$=104.2280(10)$^{\circ}$, V=2092.2(2) ${\AA}^3$, Z=4. Crystal structure of 1 reveals a syn-anti carboxylate-bridged dinuclear complex, in which the coordination environment around each copper atom exhibits a distorted square-pyramid and a distorted square plane, respectively.

• Journal of the Korean Chemical Society
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• v.39 no.7
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• pp.530-537
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• 1995

The neutral complexes $MCl_3(phda)(MeCN)]$ and $[MCl_3(PPh_3)_2(MeCN)]$ (M=Mo, V) were prepared by the reaction of $MCl_z$, (M=Mo; z=5, M=V; z=3) with N, P-donating ligands in acetonitrile solution. Addition of AgClO_4$ to these neutral monomeric complexes in acetone solution afforded $MCl_{3-n}L_2(MeCN)(S)_n](ClO_4)_n$ (n=1, 2 : s=solvent). Two types of asymmetrical homo- and hetero-dinuclear complexes have been synthesized. The type of chloride bridged dinuclear complex is $[(MeCN)(phda)ClM({\mu}-Cl)_2M'Cl(PPh_3)_2(MeCN)](ClO_4)_2.$ And the type of pyrazine bridged complex is $[(MeCN)(phda)Cl_2M({\mu}-pyz)M'Cl_2(PPh_3)_2(MeCN)](ClO_4)_2.$ These complexes were characterized by elemental analysis, $^1H,\;^13C$ NMR, IR, Far-IR and UV-Vis spectroscopy.