• Bulletin of the Korean Chemical Society
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• v.22 no.3
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• pp.311-314
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• 2001

• Bulletin of the Korean Chemical Society
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• v.20 no.6
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• pp.648-652
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• 1999

Studies have been carried out on the unusual molecular nonrigidity of CoⅢ(PymS)3 and Cp* RhⅢ(PymS)2(PymS:2-mercaptopyrimidine). The crystal structure of CoⅢ(PymS)3 approximates to an octahedral mer isomer with 4-membered N-Schelating fashion. For Cp*RhⅢ(PymS)2, one PymS ligand bonds to the rhodium ion in an S-monodentate mode (Rh-S(2) = 2.366(1)Å) while the other ligand chelates to the metal ion in an N,S-bidentae mode (Rh-S(1)=2.414(1);Rh-N(1)=2.103(3)Å). Even though the conformations and configurations of both complexes are still retained in solution, an unusual nonrigidity for the protons of the PymS region is obsered in the solution. The broad proton signals of CoⅢ(PymS)3 exhibit a temperature-dependence in the range of -40∼40℃ with a free energy of activation ΔG=64.49kJ/mol(40℃). For Cp*RhⅢ(PymS)₂,such a fluxionality has been markedly observed in solution. This fluxional behavior can be explained in terms of "ligand tautomerism" in metal complexes containing potential tautomeric forms.

• The Korean Journal of Food And Nutrition
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• v.10 no.1
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• pp.53-59
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• 1997

In this study investigated the effect of cytosine deaminase activity from Aspergillus fumigatus IFO 5840 by cytosine analogues. The results were as follows. The enzyme was strongly inibited by 2-thiouracil, 2-thiocytosine, 6-azacytosine and 2-mercaptopyrimidine. The half inhibitory concentration(HIC) of 2-thiocytosine and 6-azacytosine on cytosine deaminase was 0.80mM and 1.15mM, respectively. The enzyme was inhibited at a certain level by addition of 2-thiocytosine immediately, but was maintained to some extend under the inhibited state by 6-azacytosine in proportion to reaction time. Regardless of kinds of substrate such as cytosine and 5-fluorocytosine, 2-thiocytosine and 6-azacytosine showed action as inhibitors, 2-thiocytosine inhibited cytosine deaminase activity about twice as strong as 6-azacytosine. The enzyme, when cytosine was used as a substrate, was revealed the pattern of competitive inhibition by 2-thiocytosine and 6-azacytosine, The ki value for these compounds was 4.5$\times$10-4M and 1.756$\times$10-3M, respectively. At this point, the Hill coefficient for cytosine, 2-thiocytosine and 6-azacytosine was 1.80, 1.81 and 2.45, respectively.

• Analytical Science and Technology
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• v.5 no.1
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• pp.41-49
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• 1992

An attempt was made to prepare two series of tetrakis eight-coordinate tungsten(IV) and cerium(IV) complexes containing the 5,7-dichloro-8-quinolinol(N:${\pi}$-acceptor atom, O:${\pi}$-donor atom) ligand. Tetrakis eight-coordinate tungsten(IV) complex of 2-mercaptopyrimidine(N:${\pi}$-acceptor atom, S:${\pi}$-donor atom) ligand have also been prepared. And the new series of mixed-ligand eight-coordinate tungsten(IV) complexes containing bidentate ligands 5,7-dichloro-8-quinolinol and 2-mercaptopyrimidine have been prepared, isolated by TLC and characterized. $W(dcq)_4$, $W(dcq)_3(mpd)_1$, $W(dcq)_2(mpd)_2$, $W(dcq)_1W(dcq)_3$ and $W(mpd)_4$ complexes of MLCT absorption band appeared to 710nm, 680nm, 625nm, 581nm, and 571nm(${\varepsilon}\;max={\sim}>{\times}10^4$) on low-energy respectively. The specific absorption wave length of $Ce(dcq)_4$ is appeared 520nm(${\varepsilon}\;max={\sim}>{\times}10^4$). The Chemical shift values by proton of coordinated position appeared to $W(dcq)_4$ [$H_2:8.9ppm$]; $W(dcq)_3(mpd)_1$ [$H_2:9.3$,$H_6:9.2ppm$]; $W(dcq)_2(mpd)_2$ [$H_2:9.7$,$H_6:8.95ppm$]; $W(dcq)_1(mpd)_3$ [$H_2:9.8$,$H_6:9.4ppm$]; $W(mpd)_4$ [$H_6:8.8ppm$]; $Ce(dcq)_4$ [$H_2:9.3ppm$] with $^1H$-NMR. The inertness of mixed-ligand eight coordinate tungsten(IV) complexes have been investigated by UV-Vis. spectroscopic method in dimethylsulfoxide at $90^{\circ}C$. The inertness of $W(dcq)_n(mpd)_{4-n}$ complexes showed the following order, $W(dcq)_3(mpd)_1;k_{obs.}=3.8{\times}10^{-6}$ > $W(mpd)_4;k_{obs.}=6.0{\times}10^{-6}$ > $W(dcq)_4;k_{obs.}=6.4{\times}10^{-6}$ > $W(dcq)_2(mpd)_2;k_{obs.}=7.0{\times}10^{-6}$ > $W(dcq)_1(mpd)_3;k_{obs.}=1.7{\times}10^{-5}$, which showed the inertness until 16days, 10days, 9days, 8days, and 4days. The $W(mpd)_4$ is very inert as $k_{obs.}=3.6{\times}10^{-6}$(16days) in xylene at $90^{\circ}C$ and $k_{obs.}=6.0{\times}10^{-6}$(10days) in DMSO at $90^{\circ}C$.

• Analytical Science and Technology
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• v.6 no.5
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• pp.417-424
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• 1993

Eight-coordinate tetrakis molybdenum(IV) complexes containing 5,7-dichloro-8-hydroxyquinolinol(Hdcq) and 2-mercaptopyrimidine(Hmpd) has been prepared. $Mo(mpd)_4$, $Mo(dcq)(mpd)_3$, $Mo(dcq)_2(mpd)_2$, $Mo(dcq)_3(mpd)$ and $Mo(dcq)_4$ complexes have been isolated by thin-layer chromatography on silicagel plates. These complexes have been charaterized by $^1H-nmr$ spectrum and UV-Vis. spectrum. The chemical shift values of the protons ${\alpha}$ to the nitrogen in the ligands are shifted to down field. The relative intensities of the peaks which are positioned at the same proton of $Mo(dcq)(mpd)_3$ and $Mo(dcq)_3(mpd)$ are observed in 2:1 ratio, in case of $Mo(dcq)_2(mpd)_2$ appears in approximately a 1:1 ratio. The stereochemistry of the complexes in discussed in terms of their nmr spectrum and Orgel's rule. By vertue of the intensities (${\varepsilon}$>10,000~25,000) the low energy($16,600{\sim}19,800cm^{-1}$) bands are observed for the electronic spectra of the complexes are assigned as charge transfer bands.