• Bulletin of the Korean Chemical Society
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• v.22 no.1
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• pp.30-36
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• 2001

The crystal structures of fully dehydrated $Pd^{2+}$ - and $TI^{+}$ -exchanged zeolite X, $Pd_{18}TI_{56}Si_{100}Al_{92}O_{384}(Pd_{18}TI_{50-}X$, a = $24.935(4)\AA$ and $Pd_{21}TI_{50}Si_{100}Al_{92}O_{384}(Pd_{21}TI_{50-}X$ a = $24.914(4)\AA)$, have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd3 at $21(1)^{\circ}C.$ The crystals were prepared using an exchange solution that had a $Pd(NH_3)_4Cl_2\;:TINO_3$ mole ratio of 50 : 1 and 200 : 1, respectively, with a total concentration of 0.05M for 4 days. After dehydration at $360^{\circ}C$ and 2 ${\times}$$10^{-6}$ Torr in flowing oxygen for 2 days, the crystals were evacuated at $21(1)^{\circ}C$ for 2 hours. They were refined to the final error indices $R_1$ = 0.045 and $R_2$ = 0.038 with 344 reflections for $Pd_{18}Tl_{56-}X$, and $R_1$ = 0.043 and $R_2$ = 0.045 with 280 reflections for $Pd_{21}Tl_{50-}X$; I > $3\sigma(I).$ In the structure of dehydrated $Pd_{18}Tl_{56-}X$, eighteen $Pd^{2+}$ ions and fourteen $TI^{+}$ ions are located at site I'. About twenty-seven $TI^{+}$ ions occupy site II recessed $1.74\AA$ into a supercage from the plane of three oxygens. The remaining fifteen $TI^{+}$ ions are distributed over two non-equivalent III' sites, with occupancies of 11 and 4, respectively. In the structure of $Pd_{21}Tl_{50-}X$, twenty $Pd^{2+}$ and ten $TI^{+}$ ions occupy site I', and one $Pd^{2+}$ ion is at site I. About twenty-three $TI^{+}$ ions occupy site II, and the remaining seventeen $TI^{+}$ ions are distributed over two different III' sites. $Pd^{2+}$ ions show a limit of exchange (ca. 39% and 46%), though their concentration of exchange was much higher than that of $TI^{+}$ ions. $Pd^{2+}$ ions tend to occupy site I', where they fit the double six-ring plane as nearly ideal trigonal planar. $TI^{+}$ ions fill the remaining I' sites, then occupy site II and two different III' sites. The two crystal structures show that approximately two and one-half I' sites per sodalite cage may be occupied by $Pd^{2+}$ ions. The remaining I' sites are occupied by $TI^{+}$ ions with Tl-O bond distance that is shorter than the sum of their ionic radii. The electrostatic repulsion between two large $TI^{+}$ ions and between $TI^{+}$ and $Pd^{2+}$ ions in the same $\beta-cage$ pushes each other to the charged six-ring planes. It causes the Tl-O bond to have some covalent character. However, $TI^{+}$ ions at site II form ionic bonds with three oxygens because the super-cage has the available space to obtain the reliable ionic bonds.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.996-1002
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• 1999

The oxalate precipitation of lanthanide and actinide by oxalic acid was investigated in the simulated radioactive liquid waste, which was composed of 17 elements of alkali, alkaline earth(Cs, Rb, Ba, Sr), transition metal(Zr, Fe, Mo, Ni, Pd, Rh), lanthanide(La, Y, Nd, Ce, Eu) and actinide(Np, Am) in nitric acid solution. The effect of concentrations of nitric acid and ascorbic acid on the precipitation yield of each element in the simulated solution was examined at 0.5 M oxalic acid concentration. The precipitation yields of the elements were usually decreased with nitric acid concentration, nevertheless, the precipitation yields of lanthanide and actinide were more than 99%. Palladium was precipitated due to the reduction of Pd(II) into Pd metal by the addition of ascorbic acid in the oxalate precipitation and then, the precipitation yields of Mo, Fe, Ni, Ba decreased by 10~20% with concentration of ascorbic acid. The reductive precipitation of Pd(II) into Pd metal by the addition of ascorbic acid into the simulated radwaste occurred at below 1 M nitric acid concentration and its yield showed maximum at the ascorbic acid concentration of 0.01~0.02 M. The hydrazine suppressed the reductive precipitation of Pd by the ascorbic acid.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2711-2716
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• 2011

para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)($OC_6H_4$-p-X) (NCN = 2,6-$(CH_2NMe_2)_2C_6H_3$; X = $NO_2$ (1), Me (2)) were prepared by the reaction of Pd(NCN)($OSO_2CF_3$) with equi-molar amount of $NaOC_6H_4$-p-X. Treatment of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4$-p-Me affords the hydrogen-bonding adduct complex 3 ($2{\cdot}HOC_6H_4$-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free $HOC_6H_4$-p-Me. Complex 1 does not undergo adduct formation with $HOC_6H_4-p-NO_2$ neither from metathesis reaction of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4-p-NO_2$ nor from treatment of 1 with free $HOC_6H_4-p-NO_2$. Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes ${\sigma}$-ligand exchange reaction with $HOC_6H_4-p-NO_2$ to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective $pK_a$ values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product $PhOC_6H_4$-p-Me which was identified by GC/MS spectroscopy.

• Applied Chemistry for Engineering
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• v.17 no.6
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• pp.633-637
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• 2006

In this study, the efficient large-scale synthetic route for itraconazole, triazole antifungal agent, was developed. The original synthetic route for medicinal chemistry reported by Janssen Pharmaceutica was linear (14 linear steps) starting from 2,4-dichloroacetophenone with the total yield of 1.4%, and potential hazardous materials such as methanesulfonyl chloride ($CH_{3}SO_{2}Cl$), hydrogen gas, and sodium hydride (NaH) were used. Furthermore, the expensive 1-acetyl-4-(4-hydroxyphenyl)piperazine and palladium were used in this medicinal chemistry route, thus the manufacturing cost would be practically high. In order to improve the commercial route, we developed the process of 12 step convergent synthesis combining two intermediates which are roughly halves of itraconazole with the total yield of 12.0%, and hazardous materials and expensive reagents were excluded in this process, thus the manufacturing cost could be cut down to a great extent.

• Bulletin of the Korean Chemical Society
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• v.23 no.12
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• pp.1754-1758
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• 2002

Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

• Restorative Dentistry and Endodontics
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• v.19 no.2
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• pp.534-548
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• 1994

The purpose of this study is to observe the corrosion characteristics of seven dental amalgams (CAULK FINE CUT, CAULK SPHERICAL, OPTALLOY II, DISPERSALLOY, HI VERALOY, TYTIN, VALIANT) through the anodic polarization curve obtained by using a potentiostat. After each amalgam alloy and Hg being triturated, the triturated mass was inserted into the cylindrical metal mold, and condensed by hydrolic pressure(160 kg/$cm^2$). Each specimen was removed from the metal mold. 24 hours after condensation, specimens were polished with the emery paper and stored at room temperature for 1 week. The anodic polarization curves were employed to compare the corrosion behaviours of the amalgam in 0.9% saline solution, Fusayama's artificial saliva, and stimulated parotid saliva at $37^{\circ}C$ with 3-electrode potentiostat. After the immersion of specimen in electrolyte for 1 hour, the potential scan was begun. The potential scan range was. -1700m V ~ + 400m V(vs. S. C. E) in the working electrode and the scan rate was 50m V /sec. The results were as follows, 1. The corrosion potential, the potential of anodic current peak, and transpassive potential in the stimulated parotid saliva shifted to more anodic direction than those in saline solution, and the current density in the stimulated parotid saliva was lower than that in saline solution. Those in Fusayama's artificial saliva was similar to those in stimulated parotid saliva. 2. The anodic polarization profiles in Fusayama's artificial saliva and stimulated parotid saliva indicated a region of slow slope current density, which is extending from the corrosion potential to the potential of anodic current peak, but that in 0.9% saline solution indicated no region of slow slope. 3. The corrosion potentials for CAULK FINE CUT, CAULK SPHERICAL, and OPT ALLOY II had the similarity in 0.9% saline solution, Fusayama's artificial saliva and stimulated parotid saliva, but those for high coper amalgam and VALIANT had no similarity. 4. The current density for TYTIN amalgam in stimulated parotid saliva was the lowest among the others. 5. As for current density, there was no significant difference between palladium enriched VALINAT and other high copper amalgams.