$CH_3OH$ 용매에서 란탄족 원소 {Ln(III)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조리간드 간의 화학평형(제3보); 두자리 리간드(주게원자:N혹은 O)를 중심으로 고찰

변종철,박유철,한충훈,Byun, Jong-Chul,Park, Yu-Chul,Han, Chung-Hun 대한화학회 2000 대한화학회지 Vol.44 No.2

2-hydroxy-3-hydroxymethy1-5-methylbenzaldehyde(HHMMB)와 ethylenediamine 혹은 1,3-dia-minopropane의 축합반응에 의해 6-배위 칸막이 리간드, $H_4L[A]$와 $H_4L[B]$를 각각 얻은 후에 거대비고리 리간드 착물, $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH를 합성하였다. 2,6-diformyl-p-clesol (DFPC)로부터 합성한 Ln-거대고리([20]DOTA)착물,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy를 methanol 용매에 2일 정도 정치함으로써 [Ln([20]DOTA)($NO3$)($CH_3OH)]^{2+}$을 얻을 수 있다. 이 lanthanide-[20]DOTA착물에서 배위된 $CH_3OH$이 주게원자가 N 혹은 O인 두자리 보조리간드, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalic acid, malonic acid, acethyl-acetone에 의해 치환될 때 평형상수(K)를 $25^{\circ}C\;{\mu}=0.1M\;NaClO_4$ 에서 분광학적 방법으로 결정하였다. 보조리간드의 $pK_a$는 o-Phenylenediamine < 1,10-ptlenanthroline < ehylenediamine,oxalic acid < malonic acid < acethylacetone이며, 이때 평형상수, K는 ethylenediamine < 1,10-phenanthroline < o-phenylenediamine,acethylacetone < malonic acid < oxalic acid 경향으로 변하였다. Macroacyclic transition metal complexes such as $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH were prepared from the corresponding hexadentate compartmental ligands, $H_4L[A]$ and $H_4L[B]$, which were obtained by the condensation of 2-hydroxy-3-hydroxymethy1-5-methyIbenzaldehyde(HHNNB) and ethylenediamine or l,3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy, which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln([20] DOTA)($NO_3)(CH_3OH)]^{2+}$ was formed The equilibrium constants (k) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalicacid, malonic acid, acethylacetone) were determined by spectroscopic method at $25^{\circ}C$ and 0.1M $NaClO_4$.The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1,10-phenanthroline < ethylene-diamine, oxalic acid < malonic acid < acethylacetone. However, the equilibrium constant(K) has shown thetrend of ethyleneiamine < 1,10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid.

무·유기 오염물질의 제거를 위한 란탄족(III)이온 : 거대고리 착물의 합성

변종철,김구철,박신복 제주대학교 환경연구소 1997 환경연구논문집 : 제주대 Vol.5 No.-

CH₃OH 용매에서 란탄족 원소 {Ln(Ⅲ)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조리간드 간의 화학평형(제3보) : 두자리 리간드(주게원자 : N 혹은 O)를 중심으로 고찰 Study of the Coordination of Nitrogen- or Oxygen-Containing Bases

卞鐘轍,朴裕哲,韓忠勳 濟州大學校 基礎科學硏究所 2001 基礎科學硏究 Vol.14 No.1

2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde(HHMMB)와 ehylenediamine 혹은 1,3-diaminopropane의 축합반응에 의해 6 배위 칸막이 리간드, H₄L[A]와 H₄L[B]를 각각 얻은 후에 거대비고리 리간드 착물, Cu(H₂L[A]·H₂O, Cu(H₂L[B])·H₂O, CuFe(L[A])(NO₃)·4H₂O, CuFe(L[B])(NO₃)·4H₂O, [CuGd(H₂L[A])(NO₃)₂](NO₃)·2CH₃OH, [CuGd(H₂L[B])(NO₃)₂](NO₃)·2CH₃OH를 합성하였다. 2,6-diformyl-p-cresol(DFPC)로부터 합성한 Ln-거대고리([20]DOTA) 착물, [Ln([20]DOTA)(NO₃)(H₂O)](NO₃)₂·xH₂O{Ln(III)=Pr,Sm,Gd,Dy]를 methanol 용매에 2일 정도 정치함으로써 [Ln([20]DOTA)(NO₃)(CH₃OH)]^(2+)을 얻을 수 있다. 이 lanthanide-[20]DOTA착물에서 배위된 CH₃OH이 주게원자가 N 혹은 O인 두자리 보조리간드, L_(a)(=o-phenylenediamine, 1, 10-phenanthroline, ethylenediamine, oxalic acid, malonic acid, acethyl-acetone)에 의해 치환될 때 평형상수(K)를 25℃ μ=0.1M NaClO₄에서 분광학적 방법으로 결정하였다. 보조 리간드의 pK_(a)는 o-phenylenediamine<1, 10-phenanthroline<ethylenediamine, oxalic acid<malonic acid<acethylacetone이며, 이때 평형상수, K는 ethylenediamine<I,10-phenanthroline<o-phenylenediamine, acethylacetone<malonic acid<oxalic acid 경향으로 변하였다. Macroacyclic transition metal complexes such as Cu(H₂L[A]·H₂O, Cu(H₂L[B])·H₂O, CuFe(L[A])(NO₃)·4H₂O, CuFe(L[B])(NO₃)·4H₂O, [CuGd(H₂L[A])(NO₃)₂](NO₃)·2CH₃OH, [CuGd(H₂L[B])(NO₃)₂](NO₃)·2CH₃OH were prepared from the corresponding hexadentate compartmental ligands, H₄L[A] and H₄L[B], which were obtained by the condensation of 2-hydroxy-3-hydroxymethyl-5-methylbenzaldehyde(HHMMB) and ethylenediamine or 1.3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)(NO₃)(H₂O)](NO₃)₂·xH₂O{Ln(III)=Pr,Sm,Gd,Dy], which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln[20]DOTA)(NO₃)(CH₃OH)]^(2+) was formed. The equilibrium constants(K) for the substitution of coordinated CH₃OH in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, L_(a)(=o-phenylenediamine, 1, 10-phenanthroline, ethylenediamine, oxalic acid, malonic acid, acethyl-acetone) were determined by spectroscopic method at 25℃ and 0.1M NaClO₄. The pK_(a) of auxiliary ligands is in the order of o-phenylenediamine<1, 10-phenanthroline<ethylenediamine, oxalic acid<malonic acid<acethylacetone. However, the equilibrium constant(K) has shown the trend of ethylenediamine<I,10-phenanthroline<o-phenylenediamine, acethylacetone<malonic acid<oxalic acid.

고등학교 과학 교과 단위수 적절성에 대한 고찰 : 화학 관련 탐구·실험 학습 사례

변종철,이우환,한충훈,문대훈 제주대학교 사범대학 2002 백록논총 Vol.4 No.1

Metalloporphyrin M=Ni², Cu², Zn² 착물과 중성 리간드간의 반응에서 온도와 용매의 영향

卞鍾轍 제주대학교 1992 논문집 Vol.34 No.-

. The axial ligation of nitrogenous base (pyridine,imidazloe,1-methylimidazle,2,6-lutidine) to the four coordianted metallo-tetrakis(ortho-chlorophenyl)porphyrin and metallotetraphenylporphyrin are studied in a noncoordianting solvent,dichloromethane. Eqilibrium constants for the ligation reactions of metalloporphyrin were detrmined using the spectrophotometric method. The order of the coordination capability of the ligands was given by: 1-Methylimidazole >Imidazole>Pyridine>2,6-Lutidine. For the eqilibria of reactions of ZnTPP and Zn(o-Cl)TPP with polar solvents(DMF,DMSO),the equilibrium constants (logK)were 2.74 and 1.39 for DMSO,and 1.89 and 1.22 for DMF. Nitrogenous bases (1-Melm,Im,Py,2,6-Lut) to four coordinated Zn(o-Cl) TPP and ZnTPP have been investigated in various solvents, dimethylformanide, dimethylsulfoxide, dichloromethane,acetone, and chloroform at several temperature(15,25 and 35?). The values of thermodynamic parameter, ??(kcal/mol) and ??(eu) were determined from the temperature effect on the equilibrium constants. In addition to the temperature effect,the solvent effects on the equilibrium constants of ligation reaction were discussed. For the case of a coordinating solvents(DMSO and DMF),the solvent effects on the equilibrium reaction between the metalloporphyrin and nitrogenous base were able to explain in terms of a competition between the nitrogenous bases and solvent for the vacant coordination site of ZnTPP and Zn(o-Cl)TPP.

전이금속(Ru³+, Ni²+, Cu²+, Pd²+)-Polyaza(N₄)착물의 합성과 올레핀 산화반응에 대한 촉매적 활성

朴裕哲,金聖洙,羅勳吉,李東徹,申相姬,卞鍾轍 濟州大學校 基礎科學硏究所 1994 基礎科學硏究 Vol.7 No.1

N₄-polydentate 리간드(meso-Me₄-[14]-ane. rac-Me6-[14]-ane, 및 cyclam)의 Ru(III), Ni(II), Cu(II), 및 Pd(II) 금속이온 착물을 합성하여 NaOCl, H₂O₂, t-BuOOH, 및 PhlO등의 산화제를 사용하므로서 몇 가지 올레핀 산화반응에서 각 착물의 촉매적 환성과 선책성을 연구하였다. substrate (cyclohexene. 1-hexene, cyclooctene, 1-octene, 및 styrece)의 산화반응 생성물질은 가스 크로마토그래프 방법으로 확인하였다. Ru(III)-N₄착물은 올레핀의 촉매적 산화반응에서 산화제로 NaOCl을 사용하였을 때, 생성물질 epoxide에 대하여 상당히 높은 선택성을 나타내었다. Ru(III)-N₄착물의 촉매적 활성도는 N₄-polydentate 리간드의 flexibility, 껴(III)-Cl의 결합 상호작용 및 산화제의 입체적 효과에 따라 고찰하였다. Ni(II)-, Cu(II)-(mcso-Me6-[14]-ane) 착물의 촉매적 기능은 산화제로 PhIO를 사용한 1-octene의 산화반응에서 살펴 보았으며, 이 산화반응에서 Pd(II) 착물이 Ni(II) 및 Cu(II) 착물들보다 훨씬 높은 활성을 나타내었다. The Ru(III), Ni(II), Cu(II), and Pd(II) complexes of N₄-polydentate ligands(meso-Me6-[14]-ane. ra-Me₄-[14]-ane. and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H₂O₂, t-BuOOH, and PhlO studied. The oxidations of cyclohexene. 1-hexene, cyclooctene, 1-octene. and styrene as substrates have been investigated gas chromatographically. The Ru(III)-N₄complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(III)-N₄complexes were discussed in terms of the flexibility of N₄-polydentate ligands, the Ru(III)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhlO as oxidant was carried out to verify. The Pd(II) complex turned out to be more active catalyst than the Ni(II)complexes.

Mn(Ⅲ) Chloro-Salen형 리간드 착물의 합성과 특성

변종철,한충훈,박유철,이남호,백종석,Byeon, Jong Cheol,Han, Chung Hun,Park, Yu Cheol,Lee, Nam Ho,Baek, Jong Seok 대한화학회 2002 대한화학회지 Vol.46 No.3

Cl- 이온을 포함하는 일련의 salen형 착물 {[Mn(III)($L_{acn}$)CI]: n=1~11} 들은 $Mn(CH_3COO)_2{\cdot}4H_2O$와 네자리 칸막이 리간드 {$H_2L_{acn}$}로 부터 얻었다. 이 salen형 리간드는 diamine류 {ethylenediamine, 1,3-propnediamine, 2,2-dimethyl-1,3-propanediamine, o-phenylenediamine}와 aldehyde류 {salicylaldehyde, 5-chlorosalicyladehyde, 3,5-dichlorosalicyladehyde, 3,5-di-tert-butyl-2-hydroxybenzaldehyde}를 lmethanol 용액에서 축합반응시켜 합성하였다. 이들 리간드 및 착물들은 원소 분석, 전도도, 열분석법 및 UV-VIS IR, NMR 분광학법 등을 이용하여 확인 고찰하였다. Aseries of novel salen-type complexes {[Mn(III)($L_{acn}$)CI]: n=1~11} containing CI- ion were obtained by reactions of the Mn(CH$_3$COO)$_2$· 4H$_2$O with the potentially tetradentate compartmental ligand {$H$_2$L_{acn}$} prepared by condensation the of one mole of diamine {ethylenediamine, 1,3-propnediamine, o-phenylenediamine and 2,2-dimethyl-1,3-propanediamine} with two moles of aldehyde {alicylaldehyde, 5-chloro-salicylaldehyde, 3,5-dichlorosalicylaldethyde, and 3,5-di-tert-butyl-2-hydroxy-benzaldehyde} in a methanol solution. The resulting salen-type lignds and their Mn(III) complexes were identified and characterized by elemental analysis, conductivity, themogravimetry and UV-VIS, IR and NMR spectroscopy.

Synthesis and Characterization of Pr(Ⅲ)-,Sm(Ⅲ)-,Gd(Ⅲ)-,Dy(Ⅲ)-[18]HAM Complexes

정덕상,박신복,한충훈,변종철 濟州大學校 基礎科學硏究所 1998 基礎科學硏究 Vol.11 No.1

Lanthanide(III) and mercury(II) complexes of the 18-membered hexaaza Schiff base macrocycle 2,11,17,26,31,32-hexaazapentacyclo[26,2.1.1??,O??,O??] dotriaconta-1(31), 2,4,6,8,10,12,14,16(32) ,17,19,21,23,25,27,29-hexadecane([18]HAM) ahve been synthesized by the metal template condensationof phthalic dicarboxaldehyde and 2,6-diaminopyridine. Discrete mononuclear complexes [Pr([18]HAM)(NO₃)(OH)]NO₃·2H₂O,[Sm([18]HAM)(NO₃)(H₂O)(OH)]NO₃·2H₂O, [Gd([18]HAM)(NO₃)(H₂O)(OH)]NO₃·3H₂O, [Dy([18])HAM)(NO₃)₂(H₂O)₂]NO₃·2H₂O, and [Hg([18])HAM)(H₂O)₂(ClO₄)]ClO₄· ?H₂O, have been synthesized by using the respective hydrated lanthanide(Ⅲ) nitrate and mercury(Ⅱ) perchlorate as the template. The lanthanide(Ⅲ)-marcrocyclic complexes (lanthanide(Ⅲ)-[18]HAM) was decomposed by c-HClO? forming [18] HAM and liberating the lanthanide(Ⅲ) ion. Co(Ⅱ)- Ni(Ⅱ)-Cu(Ⅱ)-complexes of acyclic, potentially tridentate compartmental Schiff bases ([9]acy) complexes containing d-metal ion Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ) ion have been prepared by using metal template condensation of phthalic dicarboxaldehytde and 2,6-diaminopyridine. The complexes and macrocycle were characterized by elemental analysis, fast atom bombardment mass spectrometry, infrared spectroscopy, and molar conductivity. The template potential of the lanthanide(Ⅲ) cations of various sites in the assembly of [18]HAM is due to the flexibility of the macrocycle to adapt to the geometrical requirements of the metal ions and to the steric demands of the exocyclic ligands

Mn(Ⅲ)-Salen형 리간드 착물의 합성과 특성

변종철,한충훈,이남호,백종석 濟州大學校 基礎科學硏究所 2001 基礎科學硏究 Vol.14 No.2

diamine류 { ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediarnine, o-phenyle-nediamine}와 aldehydes { salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dichloro- salicylaldehyde, 3,5-di-tert-butyl-2-hydroxybenzaldehyde}를 methanol#액에서 축합반응시켜 네 자리 salen형 리간드(H₂L_(acn);n=1-11)를 합성하였다. 이들 리간드의 toluene(또는 methanol) 용액에 Mn(OAc)₂·4H₂O methanol용액을 첨가하고, 공기를 주입시켜[Mn(L_(acn))Cl] 착물을 얻었다. 이들 리간드 및 착물들은 원소분석, 전도도 및 NMR, IR, UV-VIS 분광학법을 이용하여 확인·고찰하였다. A series of tetradentate salen-type ligands(L_(ac)) were been prepared by condensation of diamines { ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, and o-phenylenediamine} and aldehydes {salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-di-chlorosalicylaldehyde, and 3,5-di-tert-butyl-2-hydroxybenzaldehyde} in methanol. These [Mn(L_(ac))Cl] complexes were synthesized from the reaction of toluene(or methanol) of L_(ac) with methanol solution of Mn(OAc)₂·4H₂O in the presence of air. These ligands and complexes were characterized and confirmed by elemental analysis, conductivity, NMR, IR, and UV-VIS spectroscopy.

란탄족(III)-oxaazamacrocycle 착물 합성 및 성질

변종철,한충훈,문대훈 濟州大學校 師範大學 科學敎育硏究所 1996 科學敎育 Vol.13 No.-

The synthesis of Ln^(3+)(=pr^(3+), Sm^(3+), Gd^(3+), Dy^(3+)) complexes with 2,6-diformyl4- methylphenol and 1,2-diaminobenzene in acetonitrile at ambient temperature was reported. Discrete mononuclear lanthanide(III)complexes of the type [Ln(20-DOTA)(NO_(3))(H_(2)O)](NO_(3))_(2)- nH_(2)O were obtained in 35 - 55% yield as deep brown crystalline compounds. The electronic and steric requirements of the lanthanide(III) ions appear to be resolved by coodination of four nitrogen and two oxygen donors of the macrocycle and to the oxygen donors of a bidentate chelating nitrate ion and to a water molecule. Thus the coordination number of the lanthanide(III) ions is 9. Each lanthanide(III) macrocyclic complex was characterized by elemental analysis, fast atom bombardment mass spectrometry, IR, and NMR spectroscopy.