Macrocyclic Tetraamine Research Articles

Dislocation discrimination: the interaction of zinc(II) and cadmium(II) with dibenzo-substituted macrocyclic and open-chain tetra-amines

Thermodynamic stabilities have been determined for zinc(II) and cadmium(II) complexes of a series of macrocyclic and open-chain tetra-amines; for the 14- to 16-membered macrocyclic systems a dislocation in the stability pattern occurs for zinc(II) at the 16-membered ring complex while, for cadmium(II), the dislocation occurs at the 15-membered ring species resulting in an enhanced stability difference [ZnII>CdII] for the complexes of this latter ring.

Effects of imide anions and axial donors on the stability and oxidation behavior of square-planar 13-15-membered macrocyclic tetraamine complexes of nickel(II) and copper(II)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEffects of imide anions and axial donors on the stability and oxidation behavior of square-planar 13-15-membered macrocyclic tetraamine complexes of nickel(II) and copper(II)Eiichi Kimura, Tohru Koike, Ryosuke Machida, Rieko Nagai, and Mutsuo KodamaCite this: Inorg. Chem. 1984, 23, 25, 4181–4188Publication Date (Print):December 1, 1984Publication History Published online1 May 2002Published inissue 1 December 1984https://doi.org/10.1021/ic00193a017RIGHTS & PERMISSIONSArticle Views383Altmetric-Citations88LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (973 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis and characterization of a ruthenyl (RuIVO) complex with a saturated macrocyclic tetramine

The synthesis and characteriaztion of a novel mono-oxo-ruthenium(IV)(ruthenyl) species of 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane (tmc)are described; this ruthenyl cation, together with another high-valent RuIV–NCS species of tmc, can also be generated electrochemically from trans-[Ru(tmc)Cl2]+.

Response of a Copper(II) Ion-selective Electrode in Cupric Buffers Based on Macrocyclic Polyamines

Abstract The behavior of a copper(II) ion-selective electrode at extremely low activity levels of free copper(II) was examined in copper(II) buffers based on macrocyclic triamines([9]aneN3 and [10]aneN3) and macrocyclic tetramines ([12]aneN4, [14]aneN4, and [16]aneN4). Although the electrode showed the ideal behavior in the buffers based on [12]aneN4 and [16]aneN4, non-ideal behavior was observed for the macrocyclic triamines and [14]aneN4. Thus, the macrocyclic polyamines did not always give the ideal copper(II) buffers for the electrode, in contrast to the case of acyclic polyamines. Stability constants, which were in good agreement with the reported values, could be determined only for [12]aneN4 and [16]aneN4. An application of the cyclic tetramines to complexiometry is also presented.

ChemInform Abstract: LIPOPHILIC MACROCYCLIC TETRAMINE AS SPECIFIC CARRIER OF AMINO ACID AND RELATED ANIONS

Chemischer InformationsdienstVolume 14, Issue 31 Heterocyclic Compounds ChemInform Abstract: LIPOPHILIC MACROCYCLIC TETRAMINE AS SPECIFIC CARRIER OF AMINO ACID AND RELATED ANIONS H. TSUKUBE, H. TSUKUBESearch for more papers by this author H. TSUKUBE, H. TSUKUBESearch for more papers by this author First published: August 2, 1983 https://doi.org/10.1002/chin.198331258Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue31August 2, 1983 RelatedInformation

Stereoselective C-alkylation of di-imine macrocycles: a versatile route to a series of meso-dialkyl-substituted macrocyclic tetramines

Macrocycles containing two o-iminoanilino units undergo stereoselective C-alkylation on treatment with Grignard reagents or lithium alkyls to give the meso-dialkyl-substituted macrocyclic tetra-amines.

Lipophilic macrocyclic tetramine as specific carrier of amino acid and related anions

Lipophilic macrocyclic polyamine 1, 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane, was firstly demonstrated to mediate specific transport of amino acid and related anions, especially dicarboxylates.

Application of the Edwards equation to formation of adducts of copper(II) macrocyclic tetraamine complexes with anions

Application of the Edwards equation to formation of adducts of copper(II) macrocyclic tetraamine complexes with anions

Rates of incorporation of nickel(II) into linear and macrocyclic tetra-amines in acetonitrile solvent, and comments on the macrocyclic effect

Rates of incorporation of nickel(II) into linear and macrocyclic tetra-amines in acetonitrile solvent, and comments on the macrocyclic effect

Reaction of cobalt(II) macrocyclic tetra-amine complexes with dioxygen

Low-pH equilibrium and kinetic studies on the oxygenation of [CoL]2+ complexes containing 12–(L2), 13–(L3), and 14-membered (isomeric, L4 and L5) fully saturated macrocyclic tetra-amines are reported. The ring size strongly influences the stability of the oxygenated products. The relative stability is connected with the stoicheiometry of the oxygenated complex, [(CoL)2(O2)(OH)]3+ for L2 and L3 and [(CoL)2(O2)]4+ for L5, which has been elucidated by potentiometric titration and polarographic measurements. The results for the macrocyclic systems are compared with a linear tetra-amine system (L1). The cyclic nature of the macrocycles, while serving to raise the [CoL]2+ stability, markedly lowers the O2 affinity of the complexes. Rates for the reaction of Co2+, L, and O2 in acetate buffers (yielding the dioxygen adducts) are first order in [Co2+] and also in [L], but are independent of [O2], indicating that the formation of [CoL]2+ is the slowest step in the O2 uptake. The separate reaction of [CoL]2+ with O2 is first order in [CoL2+] and also in [O2], with the second-order rate constants being ca. 104 times faster than those for the formation of [CoL]2+ under comparable conditions. The presence of the macrocyclic ligand slows down (by ca. 102 times) the overall rate of O2 uptake compared with linear totra-amine systems.

Kinetics and mechanism of displacement of zinc(II) by copper (II) in complexes of saturated macrocyclic tetra-amines

The kinetics of displacement of Zn2+ by Cu2+ from complexes of saturated 12- to 15-membered macrocyclic tetra-amines have been investigated in acetate-buffer solutions. Kinetic data support a common mechanism : [ZnL]2++ MeCO2H ⇌[Zn(O2CMe)]++ HL+(k1, k–1); HL++[Cu(O2CMe)]+→[CuL]2++ MeCO2H (k2), where the dissociation of L from Zn2+ is the slowest step. Values for k1 and k–1/k2 show good agreement with previous values obtained independently. The activation parameters for k1 and k–1 are discussed. The pre-dissociation mechanism is the same as that recently proposed for similar metal-exchange reactions in porphyrin complexes in dimethylformamide solutions.

Thermodynamic studies on the complexation reaction of copper(II) macrocyclic tetramine complexes with hydroxide ion

The relative stabilities of the red and blue forms of each of the complexes [CuL]2+ and [CuL(OH)]+(L =meso- or rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane) have been determined by a spectrophotometric method in basic solution at 25 °C and l= 0.1 mol dm–3. The factors which influence the relative stabilities are discussed.

ChemInform Abstract: KINETICS OF MACROCYCLIC TETRAAMINE REACTIONS WITH COPPER(II) TRIGLYCINE

Chemischer InformationsdienstVolume 10, Issue 10 Organoelement Compounds ChemInform Abstract: KINETICS OF MACROCYCLIC TETRAAMINE REACTIONS WITH COPPER(II) TRIGLYCINE M. KODAMA, Search for more papers by this authorE. KIMURA, Search for more papers by this author M. KODAMA, Search for more papers by this authorE. KIMURA, Search for more papers by this author First published: March 6, 1979 https://doi.org/10.1002/chin.197910316AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume10, Issue10March 6, 1979 RelatedInformation

ChemInform Abstract: METAL COMPLEXES WITH MACROCYCLIC LIGANDS. X. ON THE METAL COMPLEXATION KINETICS OF TWO N4‐MACROCYCLES CONTAINING A PYRIDINE RING

AbstractMittels pH‐Titrations‐ untersuchungen wird die Kinetik der Komplexierung der beiden Makrocyclen (I) mit Co(II), Ni(II),Cu(II) und Zn(II) gemessen.

Kinetics of ligand-displacement reactions of copper(II) complexes of deprotonated linear and macrocyclic dioxotetra-amines. Comparative studies with glycylglycylglycine and glycylglycylhistidine

The kinetics of displacement of doubly deprotonated linear (X1) and 13–15-membered macrocyclic dioxotetra-amines (X2–X4), compared with glycylglycylglycine (X5) and glycylglycylhistidine (X6), from their copper(II) complexes (all commonly expressed as [CuH–2X]) have been studied with ligands of various degrees of nucleophilicity including a linear tetra-amine (L1), macrocyclic tetra-amines (L2 and L3), or ethylenediaminetetra-acetate (edta) in borate (pH 8–9.5) or lutidine buffers (pH 6–7.5). The proposed mechanisms for X1–X4 are analogous to that reported for X6, where proton assistance is needed to aid cleavage of the non-terminal copper–imide bonds and provide open sites for nucleophilic attack. The effects of cyclization of the X ligands and ring size on the relative stability of the [CuH–2X] complexes are well manifested in the ligand-replacement kinetics. Thus, the 14-membered X3 which forms the most stable complex among X1–X6 is the most inert to the substitution reactions.

Metal Complexes with Macrocyclic Ligands. X. On the metal complexation kinetics of two N4‐macrocycles containing a pyridine ring

AbstractThe complexation kinetics of the two macrocycles 1 and 2 with Co2+, Ni2+, Cu2+ and Zn2+ have been measured by pH‐stat techniques. The rates are first order in metal and ligand concentration and depend upon the pH. This results from the different reactivities of the various protonated species of the macrocyclic tetraamines. The resolved rate constants are given in Table 2.In comparison with other 14‐membered cyclic aliphatic tetraazasystems 1 and 2 react more slowly with metal ions. This might be a consequence of the more rigid structure induced by the pyridine ring.

Solution chemistry of macrocycles. Part 1. Basicity constants of 1,4,8,11-tetra-azacyclotetradecane, 1,4,8,12-tetra-azacyclopentadecane, and 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane

The four protonation constants of the macrocyclic tetra-amines 1,4,8,11-tetra-azacyclotetradecane ([14]aneN4), 1,4,8,12-tetra-azacyclopentadecane ([15]aneN4), and 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane (Me4[14]aneN4) have been determined in 0.5M-KNO3 at 25 °C. Glass and silver/silver chloride electrodes were employed and the experimental e.m.f. values have been corrected for the liquid junction potential. The computer program MINIQUAD has been used for the calculation of the equilibrium constants. The values obtained are: [14]aneN4, log K1= 11.59, log K2= 10.62, log K3= 1.61, log K4= 2.42; [15]aneN4, log K1= 11.08, log K2= 10.38, log K3= 5.28, log K4= 3.60; Me4[14]aneN4, log K1= 9.70, log K2= 9.31, log K3= 3.09, log K4= 2.64. For the first two protonation steps the macrocyclic tetra-amines are more basic than the corresponding open-chain tetra-amines, even if the former exhibit a lower overall basicity.

Kinetic and equilibrium studies on copper(II) complexes of a 9-membered macrocyclic triamine, 1,4,7-triazacyclononane, and a 14-membered macrocyclic tetra-amine, 1,4,8,11-tetra-azacyclotetradecane

The thermodynamics and kinetics of formation of copper(II) complexes of 1,4,7-triazacyclononane (L1) and 1,4,8,11-tetra-azacyclotetradecane (L2) have been studied. The stability constants and thermodynamic parameters have been determined by a polarographic method for L1 and by the potentiometric method of Bjerrum and Nielson for L2. The complex [CuL2]2+ has log KCuL 27.2 (ΔH–30.4 kcal mol–1 and ΔS 22.4 cat K–1 mol–1) at I 0.20 mol dm–3 and 25 °C, which represents stability enhancement over the complex of the corresponding linear tetra-amine by three orders of magnitude due to more favourable entropy and enthalpy contributions. The higher frequency of the maximum of the visible absorption band indicates that the favourable ΔH term derives from an increase in Cu–N bond energy. On the other hand, the cyclization poses severe steric constraints on the complex of the triamine ligand, as manifested by a large enthalpy loss. This destabilization is barely compensated by the favourable entropy term: log KCuL 16.2, ΔH–13.0 kcal mol–1, and ΔS 30.5 cal K –1 mol–1. Kinetic studies in acetate buffers using the stopped-flow method have given the following rate laws for the complex formation at 25 °C and I 0.20 mol dm–3: for L1, d[CuL2+]/dt=kH[Cu(O2CMe)+][HL+], where kH= 106.8 dm3 mol–1 s–1; for L2, d[CuL2+]/dt=kH[Cu(O2CMe)+][HL+]+ k2H[Cu(O2CMe)+][H2L2+], where kH= 106.7 and k2H= 100.9dm3 mol–1 s–1. The rate law for the formation of [CuL2]2+ at pH 1.8–2.5 (unbuffered) and 25 °C has been determined by the polarographic method: d[CuL2+]/dt=kH′[Cu2+][HL+]+k2H′[Cu2+][H2L2+], where kH′= 106.9 and k2H′= 10–1-1 dm3 mol–1 s–1.

Equilibria and kinetics of complex formation between zinc(II), lead(II), and cadmium(II), and 12-, 13-, 14-, and 15-membered macrocyclic tetra-amines

Download options Please wait... Article information DOI https://doi.org/10.1039/DT9770002269 Article type Paper Download Citation J. Chem. Soc., Dalton Trans., 1977, 2269-2276 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Equilibria and kinetics of complex formation between zinc(II), lead(II), and cadmium(II), and 12-, 13-, 14-, and 15-membered macrocyclic tetra-amines M. Kodama and E. Kimura, J. Chem. Soc., Dalton Trans., 1977, 2269 DOI: 10.1039/DT9770002269 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Mutsuo Kodama Eiichi Kimura

Synthesis of macrocyclic tetramines by metal ion assisted cyclization reactions

Synthesis of macrocyclic tetramines by metal ion assisted cyclization reactions