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.

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.

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

[cis-Cr(III)(5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane)(L_(a))_(n)]CLO_(4)(n = 1 or 2)합성과 성질

변종철,한성빈,정덕상,임희정,한충훈 濟州大學校 師範大學 科學敎育硏究所 1995 科學敎育 Vol.12 No.1

rac-5.5.7.12.12.14-hexamethy1-1,4,8,11-tetraazacyclotetradecane hydrate : Lm·H_(2)O was prepared and separated from the corresponding meso-isomer dihydrate according to the Curtis method. The racisomer was confirmed by spectroscopic data of NMR and IR spectroscopy. To synthesize the [CrL_m(OH)₂] complex. the racemic compound purified from meso and racemic mixture was reacted with Cr(II1) salt. The complx ion species {[SrL_m(OH)_(2)]^(+): λ_(max) = 613.0(ε_(max) = 116 M^(-1)cm^(-1)), {[CrLm(OH)(H_(2)O)]^(2+) : λ_(max) = 575.0nm(ε_(max) = 133M^(-1)cm^(-1)). [CrLm(H_(2)O)_(2)]^(3+) : λ_(max) = 532.0nm (ε_(max) = 172M^(-1)cm^(-1))} obtained from pH change of [CrLm(OH)_(2)(OH)_(3)]^(+) solution were confirmed from an electron absorption spectra. The result of the distribution diagram of chemical species proves that main products in the range of solution pH ≤ 3.5 . 3.5 <pH <7, and pH ≥ 7. are [CrLm(H_(2)O)_(2)]^(3+). [CrL_(m)(OH) (H_(2)O)^(2+). and [CrL_m(OH)_(2), respectively. At P~ 2.0, we synthesized several Cr(III)-macrocyclic complexes containing various axial ligands (L_(a) : I, Br^(-), CI^(-), S_(2)O_(3)^(2-), F^(-), malonate, NCS^-, oxalate) instead of H_(2)O. [CrL_m(OH_(2))]^(3+) + L_(a) →[CrL_(m)(L_(a))_(n)]^(+)(n = 1 or 2) Cr(III)-macrocyclic complexes combined with vaious ligands on the axial position were primarily confirmed with the mass spectrum. Especially, when the axial ligands are malonate, oxalate, and S_(2)O_(3)^(2-), a possible thermal decomposition reaction and redox potential are considered as follows: ◁표삽입▷(본문을 참조하세요) As well, a spectrochemical series was drawn up on the basis of the ligand field strength obtained from electron absorption spertra of the complexes, [CrL_(m)(La)_(n)]^(p+) F^(-), CI^(-) ~Br^(-)<I^(-)<S_(2)O_(3)^(2-)<OH^(-)<H_(2)O<mal~NCS^(-) We can expect that there is three d-d transition d^(3) ion Tanabe-Sugano diagram. ◁표삽입▷(본문을 참조하세요) However, we found only two trasitions because the other transition {^(4)A_(2)_g(F)→^(4)T_lg(P) : v_(3)} is obscured by absorption arising from charge transfer transition. ◁표삽입▷(본문을 참조하세요)

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.

제7차 교육과정에 따른 중학교 과학(화학부분)교과서의 탐구활동 분석

변종철,문대훈,한충훈,이우환 제주대학교 사범대학 2001 백록논총 Vol.3 No.2

$CH_3OH$ 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.

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.