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  • 11
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XXVIIPart XXVI. Cu2+-promoted hydrolysis of carboxylic- and phosphonic-acid esters in the side chain of tetraazamacrocycles (1989)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 131-138 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray structures of the Cu2+ complexes of 1,4,8,11-tetraazacyclotetradecane derivatives with an ethylpro-pionate and diethylphosphonate group, 5 and 6, respectively, indicate that the metal ion is pentacoordinated by the four N-atoms of the macrocycle and one O-atom. In the case of 5, it is the carbonyl O-atom of the carboxylate group, whereas for 6 it is the phosphonyl O-atom of the phosphonate group. The hydrolysis kinetics of the functional group in the Cu2+ complexes with the 1,4,8,11-tetraazacyclotetradecanes 3-6 have been measured by pH-stat and stopped-flow techniques. The rate law for the hydrolysis of the carboxylates 3-5 is proportional to the complex concentration and to [OH-] up to pH 13, whereas that of the phosphonate 6 is proportional to [OH-] up to pH 11.5, becoming independent of [OH-] at pH 〉 11.5. The mechanisms of these two reactions are discussed, considering the possibility of an intra- or an intermolecular OH- attack and the results of the X-ray structure analyses.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19890720117
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  • 12
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XXVIII.Part XXVII: [1]. Structures and stabilities of the Cu2+ complexes with 1,4,7-triazacyclononane-1-acetic acid (1989)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 307-312 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potentiometric study of the complexation of 1,4,7-triazacyclononane-l-acetic acid (1) with Cu2+ (I = 0.5 (KNO3), T = 25°) indicates the presence of the species [Cu(1)], [Cu(1)OH], [Cu(1)2], and [(Cu(1))2OH], the stability constants of which are determined. The two complexes [Cu(1)]ClO4 and [(Cu(1)2)OH]ClO4 were also characterized by X-ray structure analysis. In both cases, the Cu2+ ion is in a distorted square-pyramidal arrangement, penta-coordinated by the three N-atoms of the macrocycle, an O-atom of the carboxylate, and an additional O-atom either from a second carboxylate or from an OH-, acting as a bridge between two metal centres.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19890720215
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  • 13
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XXIX.Part XXVIII: [1]. Structural and kinetic studies of two isomeric Cu2+ complexes with 1,4-dimethyl-8-[2-(2-pyridyl)ethyl]-1,4,8,11-tetraazacyclotetradecane (1989)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 313-319 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and complexation properties of 1,4-dimethyl-8-[2-(2-pyridyl)ethyl]-1,4,8,11-tetraazacyclotetra-decane (2) are described. This ligand forms with Cu2+ two complexes, one of which has been characterized by X-ray structure analysis. The structural, spectral, and kinetic studies indicate that the two Cu2+ complexes are isomers with the macrocycle in the trans-III and trans-I configuration. The rate of the interconversion of the trans-I isomer to the thermodynamically more stable trans-III species is proportional to [OH-]. A mechanism for this reaction is proposed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19890720216
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  • 14
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XXXIPart XXX: see [1].. Protonation studies and complexation properties of tetraazamacrocyclic methylenephosphonates with earth-alkali ions (1990)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 73 (1990), S. 140-148 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The three ligands 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis(methylenephosphonic acid) (1), 1,4,7,11-tetraazacyclotridecane-1,4,7,11-tetrakis(methylenephosphonic acid) (2), and 1,4,8,11-tetraazacyclotetradecane-1,4,8,1 1-tetrakis(methylenephosphonic acid) (3) have been synthesized by condensation of the corresponding macrocycles with formaldehyde and phosphorous acid. The protonation and stability constants with the earth-alkali ions have been determined at 25° and I = 0.1 M (Me4)N(NO3) by potentiometric titrations. Because of the high values of the first two protonation constants, 1H-NMR measurements were necessary to determine them. Titrations in different supporting electrolytes (NaNO3, KNO3, RbNO3, CsNO3, and Me4N(NO3)) show that their choice is of paramount importance, as the above ligands can form complexes with alkali-metal ions. The potentiometric results for the earth-alkali ions show that beside mononuclear complexes of different degrees of protonation ([MLHn], n = 0-4), also binuclear species are formed ([M2LHm], m = 0-2). It is interesting that 1 with the smallest macrocyclic ring has the greatest tendency to form binuclear complexes, which are so stable that they partially prevent the formation of the corresponding mononuclear species. For [ML], [MLH], [M2L], and [M2LH], the stability sequence is Mg2+ 〈 Ca2+ 〉 Sr2+ 〉 Ba2+, whereas for [MLH2], [MLH3], and [MLH4], the stability steadily decreases from Mg2+ to Ba2+.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19900730115
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  • 15
    Electronic Resource
    Electronic Resource
    Metal complexes of macrocyclic ligands. Part XXXVIIPart XXXVI: [1].. Synthesis of Heteroditopic Bis-macrocycles and Their Potential for Preparing Heterobinuclear Metal Complexes (1994)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 77 (1994), S. 23-35 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new and generally applicable synthetic path for the preparation of heteroditopic bis-macrocycles using tri-N-protected tetraazacycloalkanes as building blocks and bromoacetyl bromide as bridging reagent is described. In the first step, bromoacetyl bromide is used as acylating agent for one of the macrocycles, whereas in the second step it is used as alkylating agent for the second macrocycle, thus giving protected bis-macrocyclic amides (e.g. 6). After reduction of the amide moiety and deprotection, bis-azamacrocycles with an ethylene bridge are obtained (e.g. 8). The corresponding homoditopic bis-macrocycles 16 and 17 are also prepared for comparison purpose. Spectrophotometric studies indicate that bis-macrocycle 8, which consists of a 12- and a 14-membered ring, binds two metal ions with equal affinity, whereas compound 13, in which an unsubstituted (cyclam) and a trimethyl-substituted tetraazacyclotetradecane unit (Me3cyclam) are bridged, shows selective metal-ion binding. The first metal ion is always incorporated into the cyclam unit, whereas the second one binds to the Me3cyclam macrocycle. Thus, by sequential addition of two different metal ions, heterobinuclear complexes can easily be prepared. The electrochemistry of the binuclear Ni2+ complexes, studied by CV and DPV, as well as the EPR spectra of the binuclear Cu2+ complexes clearly indicate metal-metal interactions.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19940770105
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  • 16
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XLIVPart XLIII:[1] Kinetics of the Cu2+ incorporation into a macrocyclic ligand conjugated to proteins: Model studies for the d‘post-labeling’ technique (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 934-947 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the Cu2+ complexation by macrocycles 1 (4-[(l,4,8,11-tetraazacyclotetradec-1-yl)methyl]-benzoic acid) and 2 (N-propyl-4-[(1,4,8,11-tetraazacyclotetradec-1-yl)methyl]-benzamide) as well as by macrocycle 1 conjugated to bovine serum albumin (bsa) and to ribonuclease A (rnase) were studied by stopped flow techniques. For 1 and 2, the kinetics were followed in the mM range monitoring the d-d* absorption band of the Cu2+ complex. From the pH dependence of kobs, the rate law is v = [Cu2+] (kLH[LH] + kLH2[LH2]), where kLH and kLK2 are the bimolecular rate constants for Cu2+ with the diprotonated (LH2) and monoprotonated (LH1) form of the ligand, respectively. The values are kLH2 = 1.7(1) M-1s-1 and kLH = 2.3(1) 105 M-1s-1 for 1, and kLH2, = 0.28(9) M-1s-1 and kLH = 2.0(1) 105 M-1s-1 for 2. The kinetics of the Cu2+ incorporation into 1,2 and 1 conjugated to bsa and rnase, i.e., 3 and 4, respectively, were also followed using nitroso-R salt as a metal indicator in the μM range, i.e., under conditions typical for the ‘post-labeling’ technique to give radiolabeled monoclonal antibodies. In these cases, the reaction takes place between the 1:1 complex of Cu2+ with nitroso-R-salt and the macrocycle. At pH 6.5, the rates are very similar to each other indicating that the complexation properties of the macrocycle attached to a protein are not very different from those of the free ligand under comparable conditions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800325
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  • 17
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XXXVIIIPart XXXVII: [1].. Steric effects in the copper(II) and nickel(II) complexes with tetra-N-alkylated 1,4,8,11-tetraazacyclotetradecanes (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 505-513 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of tetra-N-alkylated 1,4,8,11-tetraazacyclotetradecanes have been synthesized and their complexation potential towards Ni2+ and Cu2+ studied. In the case of sterically demanding alkyl substituents, such as i-Pr, PhCH2, or 2-MeC6H4CH2, no metal complexes are formed, whereas for substituents such as Me, Et, and Pr, the metal ion is incorporated into the macrocycle. The spectroscopic properties of the Ni2+ and Cu2+ complexes in aqueous solution indicate that, depending on the sterical hindrance of the N-substituents, the complexes are either square planar or pentacoordinated. All these Ni2+ and Cu2+ complexes react with N3- to give ternary species, the stability of which have been determined by spectrophotometric titrations. The tendency to bind N3- decreases with increasing steric hindrance of the alkyl substituents. The X-ray studies of the Ni2+ complex with the macrocycle 11, substituted by two Me and two Pr groups, and that of the Cu2+ complex with the tetraethyl derivative 8 show that in the solid state, the metal ions exhibit square planar coordination with a small distortion towards tetrahedral geometry.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19950780220
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  • 18
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. Part XLIIIPart XLII [1]. Tetraazamacrocyclic nickel(II) and copper(II) complexes with aliphatic methylthio- and methoxy-substituted pendant chains (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 241-252 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 14-membered tetraazamacrocyclic Ni2+ and Cu2+ complexes of 4 (1, 4, 8-trimethyl-11-[(2-methylthio)ethyl]-1, 4, 8, 11-tetraazacyclotetradecane), 5. (1, 4-dimethyl-8, 11-bis[2-(methylthio)ethyl]-l, 4, 8, 11-tetraazacyclotetradecane), and 7 (1, 4, 8, ll-tetrakis[2-(methylthio)ethyl]-1, 4, 8, 11-tetraazacyclotetradecane), with pne, two, and four methylthio-substituted pendant chains, respectively, and the Ni2+ complex of 6 (1, 4-dimethyl-8, 11-bis (2-methoxyethyl)-1, 4, 8, 11-tetraazacyclotetradecane), with two methoxy-substituted pendant chains, were synthesized and their chemistry studied with regard to modelling F430. Solution spectra in H2O, MeCN, and DMF indicate participation of the side chain in metal coordination when the donor group is a thioether, whereas no coordination with the metal ion is observed with the ether group. Similarly the X-ray structures of the thioether-containing compounds [Ni(5)](ClO4)2, [Cu(5)](ClO4)2, and [Cu(7)](ClO4)2 show a coordination number of 5, whereas that of [Ni(6)](ClO4)2 with ether pendant chains, shows a coordination number of 4. Cyclic voltammetry of these complexes in MeCN reveals that Ni2+ is reversibly reduced to Ni+ between -0.64 and -0.77 V vs. SCE, the potential being influenced by the nature and number of the pendant chains. At more negative potentials, the thioether is cleaved, whereby a thiol is formed; the thiol is then oxidized at ca. + 0.8 V vs. SCE, when a glassy carbon electrode is used, or at ca. 0 V vs. SCE at a dropping Hg electrode. No cleavage of the ether bond in [Ni(6)](ClO4)2 is observed under similar conditions.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800122
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  • 19
    Electronic Resource
    Electronic Resource
    Metal Complexes with Macrocyclic Ligands. PartXLVPart XLIV: [1] Axial coordination tendency in reinforced tetraazamacrocyclic complexes (1997)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 80 (1997), S. 948-959 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cu2+ and Ni2+ complexes of three reinforced tetraazamacrocycles, containing a piperazine subunit and one or two alkyl substituents at the other two N-atoms have been prepared and their structural properties studied. In solution, the Ni2+ complexes are square-planar and show no tendency to axially coordinate a solvent molecule or an N3- ion. In contrast, the Cu2+ complexes change their geometry depending upon the donor properties of the solvent, being square-planar in MeNO2 and pentacoordinate in DMF. They also easily react in aqueous solution with N3- to give ternary species with pentacoordinate geometry, the stabilities of which have been determined. In the solid state, the X-ray crystal structures of three Cu2+ complexes also show both geometrical arrangements, two having a square-planar, the other one a distorted square pyramidal geometry. The difference behavior of Ni2+ and Cu2+ stems from the fact that the structural change from square-planar to square-pyramidal can easily be accomplished for Cu2+, whereas, for Ni2+, it is accompanied by an electronic rearrangement from the low-spin to the high-spin configuration. The relatively rigid ligands cannot Adapt to the somewhat larger high-spin Ni2+ion.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19970800326
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  • 20
    Electronic Resource
    Electronic Resource
    A Class of Trinuclear Clusters with Carbonyl Bridging (1980)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 63 (1980), S. 29-49 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The impetus for this work was the structure of a trinuclear complex with two carbonyl groups showing incipient triple bridging - Cp2Rh3(CO)4-. Its structure, barrier to rotation of one Rh(CO)2- piece vs. the rest of the molecule, and the nature of the bridging carbonyl interaction are analyzed. Isolobal analogies form an interesting connection between this complex and a bridged isomer of the recently synthesized carbene complexes, Cp2Rh2(CO)2CR2, one isomer of Cp2Rh3(CO)3, and hypothetical carbyne complexes Cp2Rh2(CO)2CH+,-. A general bonding model for Cp2Rh2(μ-CO)2X complexes is constructed. The model, rich in geometrical detail, allows minima for the bridging carbonyl groups bending toward and away from the bonded ligand X.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19800630105
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