• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.556-559
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M= Rh, Ir) reacts rapidly with 1,4-dicyanobenzene or 1,4-dicyano-2-butene to yield dinuclear metal complexes $[(PPh_3)_2(CO)M({\mu}-dicyanobenzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M = Rh; II: M = Ir) or $[(PPh_3)_2(CO)M({\mu}-dicyano-2-benzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (III: M = Rh; IV: M = Ir), respectively. Compounds I, II, III, and IV were characterized by $^1H$-NMR, $^{31}P$-NMR, and infrared spectrum. Dichloromethane solution of II and IV reacts with $H_2\;and\;I_2$ to yield oxidative addition complexes $[(PPh_3)_2(CO)IrX_2({\mu}-E)X_2Ir(CO)(PPh_3)_2](SO_3CF_3)_2$ (V; E = 1,4-dicyanobenzene, $X_2$ = $H_2$; VI : E = 1,4-dicyano-2-butene, $X_2$ = $H_2$; VII; E = 1,4-dicyanobenzene, $X_2$ = $I_2$). All metal complexes are bridged by the cyanide groups. Compounds Ⅴ, Ⅵ, and Ⅶ are characterized by conventional methods.

• Journal of Pharmaceutical Investigation
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• 제26권4호
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• pp.299-308
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• 1996

In order to develop the controlled release of a drug from the suppsitories, in vitro drug release and in vivo absorption in rabbits were investigated. Various suppository forms with hollow cavities, into which drugs in the form of fine powder or solid dispersion system(SDS) could be placed, were utilized. The polyvinyl alcohol(PVA) hydrogel as a base, and propranolol HCl(PPH) as a model drug were employed. In vitro drug dissolution studies showed that the dissolved amounts(%) of PPH from PPH-methylcellulose(MC)-SDS and PPH-ethylcellulose(EC)-SDS reached 100% and 63% in 4.5-hours, respectively. In the relative strength test for PVA hydrogel, PVA hydrogel became harder and more rigid when the number of freezing-thawing cycles and the ratio of PVA 2000 were increased. In vitro drug release profile revealed that the release rate(%) of PPH from PPH-EC-SDS and PPH-MC-SDS hollow type suppositories were sustained. The release amount(%) of PPH from PPH-EC-SDS hollow type suppositories was not affected by storage time, but since the use of hydrophilic MC made PPH diffuse into the hydrogel after it absorbed the water of base, the various release patterns were appeared as the storage time went by. In vivo absorption experiments with rabbits showed that PPH-EC-SDS(PPH : EC=1:3) hollow type suppository delayed the absorption of PPH, significantly. The $C_{max}$, $AUC_{0{\rightarrow}8}$ and MRT of PPH powder hollow type suppository were $196.37{\pm}5.63\;ng/ml$, 1105.26 ng/ml/min and 8.66 min, respectively. The $C_{max}$, $AUC_{0{\rightarrow}8}$ and MRT of PPH-EC-SDS(PPH : EC=1:3) were $91.30{\pm]14.14\;ng/ml$, 554.69 ng/ml/min, 235.99 min, respectively.

• Bulletin of the Korean Chemical Society
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• 제7권5호
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• pp.338-341
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• 1986

Hydrocarbon solution of $Ir(PPh_3)_2(CO)OClO_3$ reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to yield ${\bar{Ir(Ph_2PC_6H_4-o-CO)}}\;(PPh_3)_2(CO)(H)ClO_4$(1) and ${\bar{Ir(NC_6H_6NC}}C_6H_5)(PPh_3)_2(CO)(H)ClO_4$(2), respectively. The compound $Ir(PPh_3)_2N_2Cl$ also reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to give ${\bar{Ir(Ph_2PC_6H_4-o-C}}O)(PPh_3)_2(H)Cl(3)$ and $Ir(NC_6H_5NCC_6H_5(PPh_3)_2(H)Cl(4)$, respectively. Compounds 1, 2, 3, and 4 were characterized by infrared, $^1H$ NMR, $^{31}p$ NMR, UV spectra, and conductivity measurements.

• Bulletin of the Korean Chemical Society
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• 제20권1호
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• pp.85-88
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• 1999

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

• Bulletin of the Korean Chemical Society
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• 제13권2호
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• pp.158-162
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3(M=Rh$, Ir)reacts rapidly with Pyrazine or 4,4'-bipyridyl to yield dinuclear metal complexes $[(PPh_3)_3(CO)M({\mu}-pyrazine)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M= RhH; III: M=Ir) or [$(PPh_3)_2$(CO)M(${\mu}$-44'-bipyridyl)M(CO)$(PPh_3)_2](SO_3CF_3)_2$, (II: M=Rh; IV: M=Ir), respectively. Compounds, I, II, III, and IV were characterized by $^1H-NMR$, $^{13}C-NMR$, $^{31}P-NMR$, and infrared spectrum. Ethanol solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M=Rh, Ir) also reacts with $(TBA)_2$M'$(CN)_4$ (M'=Pd, Pt) to yield trinuclear metal complexes [$(PPh_3)_2$(CO)dM-NCM'$(CN)_2$CN-M(CO)$(PPh_3)_2]$ (V : M=Rh, M'=Pd; VI : M=Rh, M'=Pt; VII: M=Ir, M'=Pd; VIII: M=Ir, M'=Pt). The trinuclear metal complexes V, VI, VII, and VIII are bridged by the cyanide groups. The infrared spectrum of V, VI, VII, and VIII supports the presence of the bridged cyanide and terminal cyanide group.

• Bulletin of the Korean Chemical Society
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• 제15권11호
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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.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.372-376
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• 1987

Acetone solution of quinoline-8-carbaldehyde reacts with $[Rh(cod)(PPh_3)_2] PF_6$and $[Ir(cod)(PPh_3)_2] PF_6$ to yield $[Rh(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (1) and $[Ir(NC_9H_6CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (2), respectively. The compound $[Ir(cod)(PPh_3)_2] PF_6$ also reacts with $Ph_2PC_6H_4-o-CHO$ in the acetone / $H_2O$ mixture to give $[Ir(Ph_2PC_6H_4-o-CO)(H)(PPh_3)_2(CH_3COCH_3)] PF_6$ (3). Compounds 1, 2, and 3 were characterized by infrared, $^1H$ NMR, $^{31}P$ NMR spectra and conductivity measurement. The $^1H$ NMR spectra of 1, 2, and 3 support the presence of a terminal hydride that is cis to the phosphine. The IR band of 3 at 2185 $cm^{-1}$, which is assigned to $\nu$(Ir-H), and the hydride cleavage reaction of 3 with $CCl_4$, provide evidence for the Ir-H bond.

• Journal of the Korean Chemical Society
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• 제40권6호
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• pp.445-452
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• 1996

Catalytic hydrogenation of ketones and aldehydes by RuH(NO)$L_3$ ($L_3$: $PPh_3$, PhP($CH_2CH_2PPh_2$)$_2$(etp)) was investigated to examine the reaction mechanism and the competence of hydridonitrosyl complexes as catalysts for organic synthesis. RuH(NO)$L_3$ showed catalytic activity for the hydrogenation and the activities of catalysts were dependent on the steric and electronic factors. The less the steric demands of the substrates become, the more activity the catalysts show. For the electronic effect, the more the partial positive charge on the carbonyl carbon atom in ketones becomes and the more the double bond character of carbonyl group in aldehydes becomes, the more active the catalysts are. These results reflect the difference of reaction mechanisms of two substrates, ketones and aldehydes. Catalytic activities of RuH(NO)(etp) and RuH(NO)($PPh_3$)$_3$ in the presence of extra $PPh_3$ toward hydrogenation showed the existence of a reaction pathway accompanied with the change of the bonding modes of NO ligand. The roles of excess $PPh_3$ change with increase of the mole ratio of $PPh_3$ to catalysts; prevention of ligand dissociation from comlexes → bases → ligands. The activity of RuH(NO)(etp) was lower than that of RuH(NO)($PPh_3$)$_3$ toward the hydrogenation of the same substrates mainly due to the structural difference. These catalysts showed the selectivity toward olefin hydrogenation over carbonyl groups in the competitive reaction.

• Korean Journal of Crystallography
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• 제7권2호
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• pp.113-119
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• 1996

Reaction of Re(O)(PPh3)2Cl3,I, with 2,3,4,5,6-pentafluoroaniline (C6F5NH2), produced Re(NC6F5)(PPh3)2Cl3, II. The product has been characterized by 1H-NMR, elemental analysis, and X-ray diffraction. II crystallizes in the orthorhombic system, space group Pna21 with cell parameters a=18.763Å, b=14.737(2)Å, c=16.707(3)Å, Z=4. Least-square refinement of the structure led to an R(wR2)factor of 0.0455(0.1148) for 3319 unique reflections of I > 2σ(I) and for 174 variables.

• Bulletin of the Korean Chemical Society
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• 제13권4호
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• pp.391-395
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• 1992

Rhodium(I) and iridium(II) complexes, M(Cl$O_4$)(CO)$(PPh_3)_2$ and [M(CO)$(PPh_3)_3$]Cl$O_4$ (M = Rh, Ir), and RhX(CO)$(PPh_3)_2$ (X = Cl, Br, OH) catalyze the carbonylation of benzyl alcohols to produce phenylacetic acids under 6 atm of CO at $110^{\circ}C$ in deuterated chloroform. Benzyl alcohols initially undergo dehydration to give dibenzyl ethers which are then carbonylated to benzyl phenylacetates, and the hydrolysis of benzyl phenylacetate produces phenylacetic acids and benzyl alcohols. The carbonylation is accompanied with dehydrogenation followed by hydrogenolysis of benzyl alcohols giving benzaldehydes and methylbenzenes which are also produced by CO2 elimination of phenylacetic acids. Phenylacetic acid is also produced in the reactions of benzyl bromide with CO catalytically in the presence of Rh(Cl$O_4$)(CO)$(PPh_3)_2$ and $H_2O$, and stoichiometrically with Rh(OH)(CO)$(PPh_3)_2$ in the absence of $H_2O$.