• Journal of the Korean Chemical Society
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• v.50 no.5
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• pp.369-373
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• 2006

Arylation reactions of styrene catalyzed by Pd(CF3CO2)2-sulfides and Pd(CF3CO2)2-phosphines were investigated. The yield of trans-stilbene, the main product, increased as the basicity of the substituents on the aryl groups of the phosphines increased and the steric hindrance of the substituents decreased. The mechanism of the aryl migration of arylphosphines to styrene is proposed to involve the electrophilic attack of Pd to the phenyl group on the phosphines. The phosphine systems were found to be more effective than the sulfide ones.

• Journal of the Korean Chemical Society
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• v.25 no.3
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• pp.190-198
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• 1981

In contrast with pmr (only multiplets at ${\delta}6.6$∼7.8 ppm) spectrum of triphenyl-9-thioxanthenylphosphonium perchlorate and tri-o-methoxyphenyl-9-thioxanthenylphosphonium perchlorate, tri-n-butyl-9-thioxanthenylphosphonium perchlorate and tribenzyl-9-thioxanthenylphosphonium perchlorate showed a doublet at ${\delta}5.58$ and 5.70ppm, respectively, assigned to a methine proton. This value is slightly larger than the corresponding values (${\delta}5.05$~5.30) of 9-arylthioxanthenes but clearly differentiated from those of aromatic protons. This result implys that the downfield shift of a methine proton of triaryl-9-thioxanthenylphosphonium perchlorate is not due to inductive effects of an electron deficient phosphorus atom but paramagnetic deshielding effects by three aryl groups on phosphorus.

• 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.