Preparation and Properties of New Di-N-alkylated 14-Membered Tetraaza Macrocycles and Their Nickel(II) and Copper(II) Complexes

강신걸,송정훈,황동막,김기문,Gang, Sin Geol,Song, Jeong Hun,Hwang, Dong Mak,Kim, Gi Mun Korean Chemical Society 2000 Bulletin of the Korean Chemical Society Vol.21 No.11

New 14-membered tetraaza macrocycles 1,8-diallyl-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and 1,8-bis(n-propyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^3)$ have been prepared by direct react ion of 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^1)with$ allyl bromide or n-propyl bromide. The nickel(II) and copper(II) complexes of $L^2andL^3have$ been prepared. The macrocycles show high copper(II) selectivity against nickel(II) ion in methanol solutions containing water. The wavelengths (ca. 505 nm) of the d-d bands for the nickel(II) complexes are extraordinarily longer than those for the complexes of $L^1and$ other related di-N-alkylated 14-membered tetraaza macrocycles. Crystal structure of $[NiL^2](ClO4)_2$ shows that the average Ni-N bond distance $(1.992\AA)$ of the complex is distinctly longer than those of other related nickel(II) complexes. Effects of the N- and C-substituents on the properties of the macrocyclic compounds are discussed.

1,8-디메틸 및 1,8-디에틸-1,3,6,8,10,13-헥사아자시클로테트라데칸 니켈(II) 착화합물의 팔면체-평면사각형 평형

姜信杰,鄭守炅 大邱大學校附設 基礎科學硏究所 1988 基礎科學硏究 Vol.5 No.-

Nickel(Il) complexes of 1, 8-dimethyl-1, 3, 6, 8, 10,1 3-hexaazacyclotetradecane (L_(8)) and LS-diethyl-1,3,6,8,10, 13-hexaazacyclotetradecane(L.) exist as an equilibrium mixture of high spin, octahedral and low spin, square planar species in coordinating solvents. The equilibrium constants and thermodynamic parameters have been determined at various solutions from detailed analysis of the temperature-dependence of the electronic spectra. The octahedral-to-square planar conversion is endothermic and exoentropic. The effects of ligand structure and of solvent on the equilibrium are described.

전이금속 착화합물의 산화-환원 전위와 다른 성질과의 관계에 관한 고찰

강신걸 대구대학교 기초과학연구소 1984 基礎科學硏究 Vol.1 No.-

Redox potentials of transition-metal complexes are related to the thermodynamic stabilities of the two oxidaton states in a given ligand environment. The relations between redox potentials and other properties of transition-metal complexes are reported. It is suggested that the redox potential of transition-metal complexes is one of the important parameters in determining the other properties of the complexes. The concepts and applications of iigand constants are also discussed.

14각형 테트라아자 거대고리 니겔(II) 착물의 염기성 수용액에서의 거동 : 물 분자의 배위에 미치는 수산화 이온의 영향

강신걸,김성진,류기석 大邱大學校附設 基礎科學硏究所 1997 基礎科學硏究 Vol.14 No.1

Nickel(II) complexes of the 14-membered tetraaza macrocyclic ligands 1 and 2 exist in aqueous solutions as a mixture of the square-planar [Ni(L)12 (L = 1 or 2) and octahedral species [Ni(L)(H20)2l2'. The equilibrium for the complexes of 1 and 2 in basic aqueous solutions has been examined. The addition of hydroxide ion to aqueous solutions of [Ni(1)]'' shifts the equilibrium to the octahedral side; the role of hydroxide ion is opposite to that of other anion such as N03 , Cl , Br , or C104 , which shifts the equilibrium to the square-planar side. However, in the case of the nickel(II) complex of 2, the proportion of the octahedral species is not affected by the variation of the concentration of hydroxide ion. The roles of hydroxide ion as well as the effects of ligand structure on the solution behaviors of the nickel(II) complexes are discussed.

새로운 14각형 펜타아자 거대고리 리간드의 Ni(Ⅱ) 및 Cu(Ⅱ) 착화합물의 합성과 성질

강신걸,정수경 대구대학교 부설 과학교육연구소 1992 과학교육 Vol.5 No.-

1, 4, 8, 11-테트라아자운데칸과 포름알데히드 그리고 일차아민류의 주형축합반응으로부터 14각형의 펜타아자 거대고리 리간드인 1-메틸, 1-에틸, 1-프로필, 1-부틸, 1-(2-메틸프로필) 및 1-벤질-1, 3, 5, 10, 13-펜타아자시클로테트라데칸(A, B, C, D, E, 및 F)의 Ni(Ⅱ) 및 Cu(Ⅱ) 착화합물들을 합성하였다. 착화합물[M(L)]^(2+)(M=Ni(Ⅱ)또는Cu(Ⅱ) : L=A, B, C, D, E, 또는 F)에 있는 네 개의 이차 질소원자는 5-6-5-6킬레이트 고리 배열을 한 평면사각형 구조로 배위되어 있으며 알킬기가 배위된 삼차 질소는 배위되지 않은 상태에 있다. 이들 착화합물의 합성과 스펙트럼 및 성질들이 논의된다. 합성된 펜타아자 거댁리 리간드의 Ni(Ⅱ) 및 Cu(Ⅱ) 착화합의 성질들은 유사한 구조의 테트라아자 또는 헥사아자 거대고리 착화합물의 성질과 큰 차이를 나타내지 않는다.

14각형 헥 사아자 거대고리 리간드의 입체효과가 니켈(II)착화합물의 구리(II) 착화합물의 합성

강신걸,정수경,권재근 大邱大學校附設 基礎科學硏究所 1990 基礎科學硏究 Vol.7 No.-

Nickel(II) complexes of 14-membered hexaaza macrocyclic ligands with alkyl pendant arms, I, 8 -diethyl, I, 8-dipropyl, 1, 8-dibutyl, I, 8-bis(2-methylpropyl), and 1, 8-bis(2-ethylhexyl)-1, 3, 6, 8, 10, 13-hexaa zacyclo tetra decane (1, 2, 3, 4, 5, and 6, respectively), dissolve in the coordinating solvents acetonitrile, N, N-dimethyl-formamide(DMF), water, and dimethylsulfoxide(DMSO) to give equilibrium mixtures of the square planar [Ni(L)]" (L=1,2,3,4,5, or 6) and teragonally distorted octahedral [Ni(L) (S)2] '(S coordinating solvent). Equilibrium constants (K) and thermodynamic parameters for square planar-to-octahedral conversion have been determined from the electronic spectra. The values of K are decreased in the orders of CHsCN> DMF> I LO> DMSO for the nickel ( l[) complexes of macrocyclic ligands except 1 and 1> 2> 3> 4, 5> 6 for each solvent system. These 1 results are discussed in terms of the properties of the solvents and alkyl substi- "~ tuents atithe macrocyclic ligands.

Ni(Ⅱ), Cu(Ⅱ) 및 Co(Ⅲ) 테트라아자[14]테트라엔 거대고리 착화합물의 합성 및 특성

강신걸 대구대학교 (한사대학) 산업기술연구소 1985 産業技術硏究 Vol.4 No.-

The Ni(Ⅱ) and Cu(Ⅱ) Complexes with macrocycle 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene(MeHMe-(en)₂) are prepared by the reaction of erthylenediamine with acetylacetone. The reaction is promoted by the metal ion. The free macrocycle is separated as its dihydroperchlorate salt by the reaction of the Ni(Ⅱ) complex with perchloric acid. The synthesis of the Co(Ⅲ) complexes with the separated macrocycle is also described.

작용기를 가진 14각형 거대고리 리간드의 니켈(II) 및 구리(II) 착화합물들의 합성

강신걸,정수경,권재근 대구대학교 기초과학연구소 1990 基礎科學硏究 Vol.7 No.-

New nickel(II) and copper(II) complexes of the 14-membered macrocyclic ligands with functional groups 1, 8-bis(2-hydroxyethyl)-1, 3, 6, 8,10,13-hexazacyclotetradecane(H) and 1, 8-bis(2-piperazinoethyl)-1, 3, 6, 8, 10, 13-hexaazacyclotetradecane( I) have been synthesised by the template condensations of ethylenediamine, formaldehyde, and appropriate amines in the presence of the metal ion. The complexes of H and I contain hydroxy ethyl pendant arms and piperazinoethyl pendant arms at the uncoordinated nitrogens of the ligands, respectiviely. [M(H)] (C104)2 (M=Ni(II) or Cu(II)), [M(H2I)] (C104)4(M=Ni(11) or Cu(11)), and [Ni (I )] (C104)2 have square planar geometry with 5-6-5-6 chelate ring sequence. The complexes are extremely stable in crystalline states and relatively stable in highly acidic solutions. Synthesis, characterization, and properties of the complexes are described.

새로운 펜타아자 거대두고리 기간드의 니켈 (II) 및 구리 (II) 착화합물의 합성과 특성

강신걸,정수경,Kang Shin Geol,Jung Soo Kyung 대한화학회 1989 대한화학회지 Vol.33 No.5

테트라에틸렌펜타아민과 포름알데히드의 주형축합반응으로부터 새로운 펜타아자 거대두고리 리간드인 1,3,6,9,12-펜타아자비시클로[10,2,1]펜타데칸(D)의 니켈(II) 및 구리(II) 착화합물 $[Ni(D)]^{2+},\;[Cu(d)]6{2+}\;그리고\;[Cu(D)Cl]^+$를 합성하였다. 거대두고리 리간드인 D에는 한 개의 이미다졸리딘 고리가 있다. $[Ni(D)]^{2+}와 [Cu(D)]^{2+}$는 5-5-5-6 킬레이트고리 배열로 된 평면사각형 구조를 이루며, 5-배위 착이온인 $[Cu(D)Cl]^+$의 구조는 그의 전자스펙트럼으로 볼 때 사각피라미드일 것으로 보인다. 이들 니켈(II) 및 구리(II) 착화합물의 합성과 확인 그리고 분광학적인 특성과 화학적인 특성이 논의된다. New nickel(II) and coppr(II) complexes of a saturated pentaaza macrobicyclic ligand $[Ni(D)]^{2+},\;[Cu(D)]^{2+},\;and\;[Cu(D)Cl]^+$, where D is 1,3,6,9,12-pentaazabicyclo[10,2,l]pentadecane, have been prepared by the template condensation reaction of tetraethylenepentamine and formaldehyde in the presence of the metal ion. The complexes contain one imidazolidine ring in the macrobicyclic ligand, D. The complexes $[Ni(D)]^{2+}\;and\;[Cu(D)]^{2+}$ have square planar geometry with 5-5-5-6 chelate ring sequence. The electronic spectra of $[Cu(D)Cl]^+$indicate that the complex has square pyramidal geometry. Synthesis, charactrization, and the spectroscopic and chemical properties of the macrobicyclic nickel(II) and copper(II) complexes are described.

거대세고리와 거대네고리 리간드의 니켈 (II) 및 구리 (II) 착물의 합성과 니켈 (II) 착물의 평면사각형-팔면체 평형

강신걸,정수경,Shin-Geol Kang,Jung Soo-Kyung 대한화학회 1991 대한화학회지 Vol.35 No.5

포름알데히드, 테트라아민류 및 디아민류의 Ni(II) 또는 Cu(II) 이온 존재하에서의 주형축합반응으로부터 헥사아자 거대세고리 및 거대네고리 리간드의 평형사각형 착물 $[M(L)]^{2+}$(M = Ni(II) 또는 Cu(II); L = 4-메틸-1,3,6,8,11,14-헥사아자트리시클로[12,2,1,$1^{8,11}$]옥타데칸(C), 1,3,10,12,15,18-헥사아자테트라시클로[6,2,1,$1^{12,15},0^{4,9}]$도코산(D), 4-메틸-1,3,6,8,12,15-헥사아자트리시클로[13,3,1,$1^{8,12}$]에이코산(F) 또는 1,3,10,12,16,19-헥사아자테트라시클로[l7,3,1,$1^{12,16},0^{4,9}]$테트라코산(G))를 합성하였다. 이들 착물의 여섯 원자 킬레이트고리에는 두개 씩의 1,3-디아자시클로펜탄 도는 1,3-디아자시클로헥산 고리가 있다. C와 F의 착물의 다섯원자 킬레이트고리에는 메틸기가 그리고 D와 G의 경우에는 시클로헥산 고리가 있다. 이들 니켈(Ⅱ) 및 구리(Ⅱ) 착물의 합성과 특성, 그리고 수용액에서의 $[Ni(L)]^{2+}+2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$의 평형에 미치는 리간드 구조의 영향이 논의 된다. Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(II) or Cu(II) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands $[M(L)]^{2+}$(M = Ni(II) or Cu(II); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,$1^{8,11}$]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,$1^{12,15},0^{4,9}]$docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,$1^{8,12}$]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,$1^{12,16},0^{4,9}]$tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(II) and Cu(II) complexes are presented. The effects of the ligand structure on the equilibrium $[Ni(L)]^{2+}2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$ in aqueous solutions are described.