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Chin, Chong-Shik,Park, Jeong-Han,Shin, Sang-Young,Kim, Choong-Il Korean Chemical Society 1987 Bulletin of the Korean Chemical Society Vol.8 No.3
Reactions of $Rh(ClO_4)(CO)(AsPh_3)_2$ with unsaturated nitriles and aldehyde, L, produce a series of new cationic rhodium (I) complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ (L = $CH_2$ = CHCN, $CH_2$ = C($CH_3$)CN, trans-$CH_3CH$ = CHCN, $CH_2$ = CH$CH_2$CN, trans-$C_6H_5CH$ = CHCN, and trans-$C_6H_5CH$ = CHCHD) where L are coordinated through the nitrogen and oxygen, respectively but not through the ${\pi}$-system of the olefinic group. Dissociation constants for the reaction, $[RhL(CO)(AsPh_3)_2]ClO_4$ $\rightleftharpoons$ $Rh(ClO_4)(CO)(AsPh_3)_2$ + L, have been measured to be $1.20{\times}10^{-4}$ M (L = $CH_2$ = CHCN), $1.05{\times}10^{-4}$ M (L = $CH_2$ = C($CH_3$)CN, $3.26{\times}10^{-5}$ M (L = trans-$CH_3$CH = CHCN) and $6.45{\times}10^{-5}$ M (L = $CH_2$ = CH$CH_2$CN) in chlorobenzene at $25^{\circ}C, and higher than those of triphenylphosphine complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ where L are the corresponding nitriles that are coordinated through the nitrogen atom. The differences in dissociation constants seem to be predominantly due to the differences in ${\Delta}H$ (not due to the differences in ${\Delta}S$). The weaker Rh-N (unsaturated nitriles) bonding in $AsPh_3$ complexes than in $PPh_3$ complexes (based on ${\Delta}H$ values) suggests that the unsaturated nitriles in 2∼5 are good ${\sigma}$-donor and poor ${\pi}$-acceptor.
Chin Chong Shik,Jung Ho Jin,Hong Seung-gweon Korean Chemical Society 1992 Bulletin of the Korean Chemical Society Vol.13 No.4
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 $H_2O$.
Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes
Chin, Chong-Shik,Won, Gyong-Shik,Song, Joong-Ho Korean Chemical Society 1994 Bulletin of the Korean Chemical Society Vol.15 No.11
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.
Chin, Chong Shik,Eum, Min-Sik,Kim, Song yi,Kim, Choongil,Kang, Sung Kwon WILEY-VCH Verlag 2006 European journal of inorganic chemistry Vol.2006 No.24
<P>A new type of iridium(III) complex [trans-Ir(ppy)<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB>]<SUP>+</SUP> (1) has been prepared by a novel synthetic method and its structural and photoluminescent characteristics have been compared with those of the cis analogue, [cis-Ir(ppy)<SUB>2</SUB>(PPh<SUB>3</SUB>)(P(OPh)<SUB>3</SUB>)]<SUP>+</SUP> (2) which has also been newly prepared in this study. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2006-2006-24-EJIC200600888-fig000.gif' alt='wiley_img/14341948-2006-2006-24-EJIC200600888-fig000'> </P>