• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.801-806
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• 2001

A study has been carried out on the separation of gold, iridium, palladium, rhodium, ruthenium and platinum in chromite samples and their quantitative determination using inductively coupled plasma atomic emission spectrometry (ICP-AES). The dissolution condition of the minerals by fusion with sodium peroxide was optimized and chromatographic elution behaviour of the rare metals was investigated by anion exchange chromatography. Spectral interference of chromium, a matrix of the minerals, was investigated on determination of gold. Chromium interfered on determination of gold at the concentration of 500 mg/L and higher. Gold plus trace amounts of iridium, palladium, rhodium and ruthenium, which must be preconcentrated before ICP-AES was separated by anion exchange chromatography after reducing Cr(Ⅵ) to Cr(III) by H2O2. AuCl4- retained on the resin column was selectively eluted with acetone- HNO3-H2O as an eluent. In addition, iridium, palladium, rhodium and ruthenium remaining on the resin column were eluted as a group with concentrated HCl. However, platinum was eluted with concentrated HNO3. The recovery yield of gold with acetone-HNO3-H2O was 100.7 ${\pm}2.0%$, and the yields of palladium and platinum with concentrated HCl and HNO3 were 96.1 ${\pm}1.8%$ and 96.6 ${\pm}1.3%$, respectively. The contents of gold and platinum in a Mongolian chromite sample were 32.6 ${\pm}$ 2.2 ${\mu}g$/g and 1.6 $\pm$ 0.14 ${\mu}g$/g, respectively. Palladium was not detected.

• Bulletin of the Korean Chemical Society
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• v.15 no.6
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• pp.432-436
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• 1994

Monomeric rhodium and iridium-diaryltetrazene complexes $Cp^*$M(RNN=NNR)($Cp^*$=1,2,3,4,5-pentamethylcyclope ntadienyl; M=Rh, Ir; R=Ph, 4-tolyl) have been synthesized from [$Cp^*MCl_2]_2$(M=Rh, Ir) and 2 equiv. of $[Li(THF)_x]_2(RN_4$R) in benzene. We have determined the crystal structure of (${\eta}^5$-pentamethylcyclopentadienyl)diphenyltetrazene iridium by using graphite-monochromated Mo-$K_a$ radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a=13.781(3), b=9.035(l), c=17.699(3) ${\AA}$, and ${\beta}=111.93(l)^{\circ}$. An X-ray crystal structure of complex 1 showed a short N(2)-N(3) distance ($1.265 {\AA}$) consistent with the valence tautomer A with Ir(III) rather than Ir(I). All complexes are highly colored and decompose on irradiation at 254 nm. Electrochemical studies show that complex 1 displays a quasi-reversible reduction.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.195-200
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• 1993

The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1945-1950
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• 2010

Solvent extraction experiments of Pt(IV), Pd(II) and Rh(III) by Alamine336 were performed from the mixed chloride solutions. In the HCl concentration range from 1 to 5 M, most of Pt and Pd were extracted from the mixed solutions. However, the extraction percentage of Rh was much smaller than that of Pt and Pd. Lower concentration of Alamine336 in strong HCl solution led to higher separation factor of Rh from Pt and Pd. Adding $SnCl_2$ to the mixed solutions increased the extraction percentage of Rh, while the extraction percentage of Pt and Pd was little affected. Our results showed that selective separation of Rh or coextraction of the three platinum group metals from the mixed solution would be possible by adjusting the extraction conditions.

• Korean Journal of Metals and Materials
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• v.48 no.5
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• pp.430-435
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• 2010

Solvent extraction experiments of Rh(III) and Ir(IV) were performed on the HCl solution by using Alamine336 and TBP. The extraction percentage of Rh and Ir by Alamine336 was much higher than that by TBP. For the solvent extraction with Alamine336, the extraction percentage of Rh and Ir decreased with a HCl concentration. However, the extraction percentage of both metals by TBP was below 12% in our experimental range and increased with an increasing HCl concentration of up to 8 M. From the mixed solution of Ir with an excess SnCl$_{2}$, most of the tin was extracted by Alamine336 and TBP. However, the extraction percentage of Ir by Alamine336 was reduced and no iridium was extracted by TBP. The extraction behavior of Ir and Sn was investigated by scrubbing experiments on the loaded Ir with a SnCl$_{2}$ solution.

• Resources Recycling
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• v.26 no.3
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• pp.26-31
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• 2017

LIX 63 showed a selectivity for the extraction of Pd(II) over other PGMs, such as Pt(IV), Ir(IV) and Rh(III) from 6 M HCl solution. Moreover, HCl solution has significant effect on the oxidation-reduction reaction between Ir(IV) and LIX 63. Therefore, the applicability of employing LIX 63 for the separation of the 4 PGMs was investigated from 3 M HCl solution. From 3 M HCl solution, only Pd(II) was selectively extracted by LIX 63 and its extraction percentage was higher than from 6 M HCl solution. Extraction of the Pd(II) free raffinate with TBP led to the selective extraction of Pt(IV). After oxidation of Ir(III) with $NaClO_3$ to Ir(IV), extraction of the Pt(IV) free raffinate with Aliquat 336 selectively extracted Ir(IV). For each extraction step, optimum stripping conditions were obtained. By this process, it was possible to separate the 4 PGMs by solvent extraction from 3 M HCl solution.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.360-362
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• 1989

Catalytic isomerization of unsaturated alcohols to the corresponding carbonyl compounds with$Rh(ClO_4)(CO)(PPh_3)_2\;(1)\;and\;[Rh(CO)(PPh_3)_3]ClO_4$ (2) is faster under hydrogen (where hydrogenation also occurs to give saturated alcohols) than under nitrogen. The isomerization under hydrogen seems to occur through an alkylhydridorhodium(III) complex which also undergoes reductive elimination to give hydrogenation products, saturated alcohols. The isomerization under hydrogen is faster with 2 than with 1, which is understood by acceleration of the last step, enol formation by $PPh_3$ dissociated from 2 and present in the reaction mixture when 2 is used as catalyst. Relative rates of the isomerization observed for different unsaturated alcohols are interpreted by steric effects of substituted groups and numbers of hydrogens to be abstracted by the rhodium of the intermediate, alkylhydridorhodium(III) to undergo the reductive elimination to give enol which is then rapidly converted into a carbonyl compound. It has been observed that the hydrogenation is relatively significant when reactions occur slowly whereas the isomerization is predominant when reactions proceed rapidly.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.961-966
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• 1994

Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.