- Phosphoric triamides. 31Phosphorus NMR chemical shift as a function of the P-N bond characteristics
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Six phosphoric triamides in which amide nitrogens are incorporated into an increasing number (from 0 to 3) of the 1,3,2-diazaphospholidin-2-one rings have been prepared and their crystal structures have been determined. The structural changes from the non-cyclic to the mono-, di- and tri-cyclic systems result in the decrease of the N-P-N bond angles and the increase of the P-N bond distance. These changes are paralleled by a strong deshielding of the 31P nucleus, leading to an exceptionally high δp value for the tricyclic derivative. The δp-structural parameters relationship is discussed in terms of the changes in hybridization of phosphorus and the variation in the P-N bond order.
- Bourne, Susan A.,Mbianda, Xavier Y.,Modro, Tomasz A.,Nassimbeni, Luigi R.,Wan, Huijie
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Read Online
- A high-nuclearity metal-cyanide cluster [Mo6Cu14] with photomagnetic properties
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A high-nuclearity metal-cyanide cluster [Mo6Cu14] has been prepared and its photomagnetic properties investigated. The photoswitchable magnetic phenomenon observed is thermally reversible (T ≈ 230 K). In the field of photomagnetism, [Mo6Cu14] represents a unique example of a nanocage and the highest nuclearity observed so far.
- Bridonneau,Chamoreau,Gontard,Cantin,Von Bardeleben,Marvaud
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Read Online
- Measurement of the rate of copper(II) exchange for 64Cu complexes of bifunctional chelators
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Measurement of the rate of loss of 64Cu from the chelators used in the preparation of 64Cu-labeled proteins is critical to the development of effective 64Cu-labeled radiopharmaceuticals. Typically, however, this assessment has been made indirectly, by comparison of the relative uptake of the labeled proteins in the liver, or under non-physiological conditions such as hot 5 M HCl. In the present study, we measured the rate of loss of 64Cu from a series of chelators (DOTA, TETA, and NOTA) that are commonly used to label proteins as a function of [Cu2+] (1, 2, and 5 μM) and pH (7.5, 6.0. and 5.0). We found that 64Cu-NOTA is somewhat more kinetically stable than 64Cu-TETA and that both 64Cu-NOTA and 64Cu-TETA are much more kinetically stable than 64Cu-DOTA. Furthermore, the rate of loss of 64Cu from Cu-DOTA increased with higher [Cu 2+] and pH while the rate of loss of 64Cu from Cu-TETA and Cu-NOTA was minimally dependent on [Cu2+] and pH. These results suggest that NOTA is preferable to TETA and DOTA for the preparation of 64Cu-labeled proteins.
- Maheshwari, Vidhi,Dearling, Jason L.J.,Treves, S. Ted,Packard, Alan B.
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Read Online
- Synthesis method of 1, 4, 7-triazacyclononane
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The invention provides a synthesis method of 1, 4, 7-triazacyclononane. The preparation method comprises the step of: carrying out condensation ring-closure reaction on N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride and ethylenediamine at low temperature to obtain 1, 4, 7-triazacyclononane. According to the method, the reaction temperature ranges from -50 DEG C to -30 DEG C, and the molar ratio of N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride to ethylenediamine is 1: (0.95-1). 4-dimethylaminopyridine (DMAP) is adopted as an acid-binding agent, and the molar ratio of the DMAP to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is (3.9-4.1): 1. Carbon tetrachloride is selected as a reaction solvent, and the mass ratio of the carbon tetrachloride to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is 2: 1. According to the process, other side reactions can be effectively avoided, the highest reaction yield can reach 78% or above, and the product purity can reach 94% or above.
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Paragraph 0010-0019
(2021/09/01)
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- DINUCLEATING LIGAND OR DINUCLEAR METAL COMPLEX
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To provide a dinuclear metal complex that can be synthesized simply and easily and has a proper anticancer action.SOLUTION: The present disclosure provides a dinucleating ligand represented by the following formula (I) and a dinuclear metal complex thereof (where X is H or a substituted carbamoyl group, R1, R2, R3, and R4 independently represent H or a C1-8 linear or branched alkyl group).SELECTED DRAWING: None
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Paragraph 0048; 0056-0057
(2021/03/19)
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- Second-Sphere Interaction Promoted Turn-On Fluorescence for Selective Sensing of Organic Amines in a TbIII-based Macrocyclic Framework
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Guided by a second-sphere interaction strategy, we fabricated a Tb(III)-based metal—organic framework (MMCF-4) for turn-on sensing of methyl amine with ultra-low detection limit and high turn-on efficiency. MMCF-4 features lanthanide nodes shielded in a nonacoordinate geometry along with secondary coordination spheres that are densely populated with H-bond interacting sites. Nonradiative routes were inhibited by binding-induced rigidification of the ligand on the second coordination sphere, resulting in luminescence amplification. Such remote interacting mechanism involved in the turn-on sensing event was confirmed by single-crystal X-ray diffraction and molecular dynamic simulation studies. The design of both primary and secondary coordination spheres of Tb(III) enabled the first turn-on sensing of organic amines in aqueous conditions. Our work suggests a promising strategy for high-performance turn-on sensing for Ln-MOFs and luminous materials driven by other metal chromophores.
- Huang, Xianqiang,Liu, Qingzhi,Liu, Shixi,Ma, Shengqian,Nafady, Ayman,Niu, Zheng,Ren, Junyu,Tsai, Chen-Yen,Ye, Yingxiang
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supporting information
p. 23705 - 23712
(2021/09/22)
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- An Efficient Synthesis of N,N,N-Substituted 1,4,7-Triazacyclononane
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A new and efficient synthetic approach is reported for various N,N,N-substituted 1,4,7-triazacyclononanes (TACN) in moderate to excellent yields, with optimization of the reaction sequences and conditions of the intermediate 1,4,7-tribenzyl-1,4,7-triazonane-2,6-dione reduction with LiAlH4, removal of benzyl with Pd/C, and alkylation reactions. This reaction scheme provides a convenient and flexible method to prepare various N,N,N-substituted TACN derivatives.
- Huang, Yong,Liu, Yajing,Liu, Song,Wu, Renbo,Wu, Zehui
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p. 1546 - 1551
(2018/04/20)
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- Synthesis methods of 1, 4, 7-triazacyclononane and derivatives thereof and obtained products
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The invention provides a synthesis method of 1, 4, 7-triazacyclononane. The synthesis method comprises the following steps: synthesizing an intermediate 1, 4, 7-tribenzyl-1, 4, 7-triazacyclononane-2,6-dione from N, N'-bis(N-benzyl-2-chloroacetamide) ethylenediamine and benzylamine as raw materials, and then reducing to remove benzyls to obtain the 1, 4, 7-triazacyclononane. The invention furthersynthesis methods of N, N', N'-1, 4, 7-triazacyclononane derivatives and corresponding products synthesized by the synthesis methods. The invention has the advantages as follows: the cost is low; theoperability is strong; N, N', N'-1, 4, 7-triazacyclononane derivatives with different substituents are selectively synthesized under a controllable reaction condition; the synthesis methods are applicable to industrial production and are applicable to synthesis of different types of triazacyclononane derivatives with different substituents; the implementation value and benefits are relatively high; the products have a potential application value in the field of radiopharmaceutical chemical multifunctional chelating agents, ion recognition, coordination chemistry and the like.
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- Comparative studies of the electronic, binding and photophysical properties of a new nona-dentate hemi-cage tripodal HQ pendant trizaza-macrocycle with unfilled, half-filled and completely filled lanthanide ions
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The present paper describes the comparative studies of the electronic, photophysical and binding properties of a new C3-symmetric polydentate ligand, 1,4,7-tris-{(5-methylene-8-hydroxyquinoline)-1,4,7-triazacyclononane} (9N3Me5Ox), and its complexes with 4f0, 4f7, and 4f14 metal ions (La3+, Gd3+, and Lu3+) by experimental and theoretical methods using DFT, TDDFT, TDDFTB, ETS-NOCV, NBO and Ligand Field DFT (LFDFT). The ligand and the complexes were synthesized and characterized through elemental analysis, molar conductance, TGA, FT-IR, FT-NMR, 1H-1H COSY and ESI-mass spectrometry techniques. The spectral data and structural studies revealed the formation of nine-coordinate compounds with the general formula [Ln(9N3Me5Ox)(H2O)3], in which the nonadentate chelator acted as a trinegative hexadentate ligand coordinating to the metal ions through three sets of O,N-donors of 8-hydroxyquinoline groups and three coordinated water molecules. The molecular modeling studies suggest that the metal ion can be easily encapsulated in its central cavity forming hemi-cage complexes without altering the basic metal-ligand coordination sphere. The nature of the bonding between the lanthanide ions and 9N3Me5Ox3?, elucidated by means of the natural bond orbital (NBO), Morokuma-Ziegler energy decomposition analysis (ETS-NOCV) scheme, suggests that the Ln-L bonds are more electrostatic (~82percent) than covalent (~18percent). The covalent character of the complexes increases in the order Lu > La > Gd. The photoluminescence spectral studies of the metal complexes revealed that the observed luminescence of the compounds in the solid state and solution is of different origin. The vibrational, 1H and 13C NMR spectral data obtained from the DFT optimized structures showed good agreement with the experimental results. The excitation and emission behaviours of the ligand and the complexes were established by molecular orbital analysis of the ground state DFT geometry as well as of the excited state optimized geometry using TD-DFT and TD-DFTB orbital analysis, excitation and emission properties.
- Baral, Minati,Kanungo, B. K.,Rohini
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p. 16040 - 16059
(2018/10/04)
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- Using iSUSTAIN to validate the chemical attributes of different approaches to the synthesis of tacn and bridged (bis)tacn ligands
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Using green chemistry principles, alternative approaches for the synthesis of commercially important aza-macrocyclic tacn and (bis)tacn derivatives have been investigated to determine the step average and overall efficiency of these synthetic methods. Based on analytical metrics derived from the iSUSTAIN toolkit, the Richman-Atkins route for the synthesis of tacn (1) was found to be the more efficient; however an alternate route was shown to be preferable for the synthesis of (bis)tacn (2) compounds. The outcome of this study documents the importance of rigorous analysis of synthetic procedures for such aza-macrocyclic compounds in terms of their green chemistry attributes, in order to delineate how alternative synthetic methods can be ranked, more innovative procedures selected to improve productivity and yield, and synthetic methods deployed to achieve greater levels of waste reduction, reduced use of hazardous chemicals and lower environmental impact.
- Coghlan,Campi,Jackson,Hearn
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supporting information
p. 5477 - 5484
(2016/10/21)
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- Efficient synthesis of 1,4,7-triazacyclononane and 1,4,7-triazacyclononane-based bifunctional chelators for bioconjugation
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The reaction of diethylenetriamine with chloroacetaldehyde yielded a bicyclic aminal intermediate for the synthesis of 1,4,7-triazacyclononane (TACN), a macrocyclic polyamine the derivatives of which find applications as catalysts, bleaching agents, and chelators for medical imaging. This new synthetic protocol outperforms the synthetic methods described so far because it does not involve any cyclization step. Moreover, this aminal intermediate allowed access to a new family of TACN derivatives functionalized on the carbon skeleton, for example, C-aminomethyl-TACN. This novel compound is a precursor of valuable bifunctional chelating agents for nuclear medicine, in particular, for the preparation of PET imaging agents after bioconjugation and metallation with 68Ga or 64Cu.
- Dsogre, Pauline,Rousselin, Yoann,Poty, Sophie,Bernhard, Claire,Goze, Christine,Boschetti, Frdric,Denat, Franck
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p. 7831 - 7838
(2015/02/02)
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- SYNTHESIS OF IMIDAZO[1,2-a]PYRAZIN-4-IUM SALTS FOR THE SYNTHESIS OF 1,4,7-TRIAZACYCLONONANE (TACN) AND N- AND/OR C-FUNCTIONALIZED DERIVATIVES THEREOF
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The present invention embodiments relate to a compound with formula (V′) The invention also relates in certain embodiments to the synthesis method for compound (V′) and its use for the preparation of 1,4,7-triazacyclononane (tacn) and N- and/or C-functionalized derivatives thereof, particularly compounds with formula (I) The invention also relates in certain embodiments to metallic complexes comprising a ligand with formula (I) and a metal and their use for imaging.
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- Triamidetriamine bearing macrobicyclic and macrotricyclic ligands: Potential applications in the development of copper-64 radiopharmaceuticals
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A versatile and straightforward synthetic approach is described for the preparation of triamide bearing analogues of sarcophagine hexaazamacrobicyclic cage ligands without the need for a templating metal ion. Reaction of 1,1,1-tris(aminoethyl)ethane (tame) with 3 equiv of 2-chloroacetyl chloride, yields the tris(α-chloroamide) synthetic intermediate 6, which when treated with either 1,1,1-tris(aminoethyl)ethane or 1,4,7-triazacyclononane furnished two novel triamidetriamine cryptand ligands (7 and 8 respectively). The Co(III) and Cu(II) complexes of cryptand 7 were prepared; however, cryptand 8 could not be metalated. The cryptands and the Co(III) complex 9 have been characterized by elemental analysis, 1H and 13C NMR spectroscopy, and X-ray crystallography. These studies confirm that the Co(III) complex 9 adopts an octahedral geometry with three facial deprotonated amido-donors and three facial amine donor groups. The Cu(II) complex 10 was characterized by elemental analysis, single crystal X-ray crystallography, cyclic voltammetry, and UV-visible absorption spectroscopy. In contrast to the Co(III) complex (9), the Cu(II) center adopts a square planar coordination geometry, with two amine and two deprotonated amido donor groups. Compound 10 exhibited a quasi-reversible, one-electron oxidation, which is assigned to the Cu2+/3+ redox couple. These cryptands represent interesting ligands for radiopharmaceutical applications, and 7 has been labeled with 64Cu to give 64Cu-10. This complex showed good stability when subjected to L-cysteine challenge whereas low levels of decomplexation were evident in the presence of L-histidine.
- Tan, Kel Vin,Pellegrini, Paul A.,Skelton, Brian W.,Hogan, Conor F.,Greguric, Ivan,Barnard, Peter J.
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supporting information
p. 468 - 477
(2014/01/23)
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- Phosphate diester cleavage, DNA interaction and cytotoxic activity of a bimetallic bis(1,4,7-triazacyclononane) zinc complex
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The dinuclear zinc complex [Zn2{bcmp(-H)}(μ-Cl)](ClO 4)2·H2O {bcmp = 2,6-bis(1,4,7- triazacyclonon-1-ylmethyl)-4-methylphenol} has been synthesized and structurally characterized. The DNA binding affinity was assessed by ethidium bromide fluorescence quenching experiments. The complex relaxes supercoiled pUC19 DNA into the nicked form at low micromolar concentration. Mechanistic studies were carried out using the DNA and RNA models bis(2,4-dinitrophenyl) phosphate (BDNPP) and 2-hydroxypropyl p-nitrophenyl phosphate (HPNP). A detailed kinetic analysis suggested that the bridging OH group of the solution species [Zn 2{bcmp(-H)}(μ-OH)]2+ acts as the nucleophile in the hydrolysis of BDNPP, while in the case of HPNP, the bridging OH group acts as a general base and seems to shift to a terminal position upon substrate coordination. Finally, the cytotoxicity profile of the dinuclear zinc(II) complex was assessed. The complex showed promising in vitro antitumour activity against pancreatic and lung cancers cell lines. A new bimetallic Zn complex with a phenolate scaffold ligand with two aza-crown binding sites has been synthesized and characterized. DNA binding, cleavage and cytotoxicity results are reported.
- Montagner, Diego,Gandin, Valentina,Marzano, Cristina,Erxleben, Andrea
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supporting information
p. 4084 - 4092
(2014/12/09)
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- Phosphate diester cleavage, DNA interaction and cytotoxic activity of a bimetallic bis(1,4,7-triazacyclononane) Zinc Complex
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The dinuclear zinc complex [Zn2{bcmp(-H)}(μ-Cl)](ClO4)2·H2O {bcmp = 2,6-bis(1,4,7-triazacyclonon-1-ylmethyl)-4-methylphenol} has been synthesized and structurally characterized. The DNA binding affinity was assessed by ethidium bromide fluorescence quenching experiments. The complex relaxes supercoiled pUC19 DNA into the nicked form at low micromolar concentration. Mechanistic studies were carried out using the DNA and RNA models bis(2,4-dinitrophenyl) phosphate (BDNPP) and 2-hydroxypropyl p-nitrophenyl phosphate (HPNP). A detailed kinetic analysis suggested that the bridging OH group of the solution species [Zn2{bcmp(-H)}(μ-OH)]2+ acts as the nucleophile in the hydrolysis of BDNPP, while in the case of HPNP, the bridging OH group acts as a general base and seems to shift to a terminal position upon substrate coordination. Finally, the cytotoxicity profile of the dinuclear zinc(II) complex was assessed. The complex showed promising in vitro antitumour activity against pancreatic and lung cancers cell lines.
- Montagner, Diego,Gandin, Valentina,Marzano, Cristina,Erxleben, Andrea
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supporting information
p. 4084 - 4092
(2015/04/27)
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- A heterogeneous, selective oxidation catalyst based on Mn triazacyclononane grafted under reaction conditions
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A unique method has been developed to synthesize an active heterogeneous oxidation catalyst by the in situ grafting of a 1,4,7-trimethyl-1,4,7- triazacyclononane manganese complex on carboxylic acid-functionalized supports serving dual roles as surface tether and necessary co-catalyst, massively increasing total turnovers as compared to the homogeneous analog.
- Schoenfeldt, Nicholas J.,Korinda, Andrew W.,Notestein, Justin M.
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supporting information; experimental part
p. 1640 - 1642
(2010/07/03)
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- Significant relaxivity gap between a low-spin and a high-spin iron(II) complex of structural similarity: An attractive off-on system for the potential design of responsive MRI probes
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We have identified a pair of structurally similar iron complexes in the oxidation state ii that exist in a low-spin and a high-spin electronic spin state in aqueous media, respectively. The low-spin, diamagnetic complex (LS, 1) is mute in MRI while the high-spin, paramagnetic complex (HS, 2) generates considerable contrast in MRI. These results demonstrate that iron(ii) complexes, hitherto neglected for contrast enhancement in MRI, have potential for the design of an MRI probe that suffers passage from one state to the other under the influence of a targeted biochemical activity and thus operates in an off-on mode. At 300 MHz (proton resonance frequency at 7 T field strength) and in phosphate buffer, we found a longitudinal relaxivity (r1) of 1.29 mM -1 s-1 for 2 that, in light of the difference in unpaired electrons of the central metal atoms (4 for FeII; 7 for Gd III), comes remarkably close to that of gadolinium(iii)-DOTA (2.44 mM-1 s-1), a commercialized MRI contrast agent. Since gadolinium complexes are always paramagnetic and can therefore not be muted in MRI, the here presented Fe(ii)-based system offers an alternative strategy to develop responsive MRI probes. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Stavila, Vitalie,Allali, Mustapha,Canaple, Laurence,Stortz, Yvon,Franc, Cecile,Maurin, Philippe,Beuf, Olivier,Dufay, Olivier,Samarut, Jacques,Janier, Marc,Hasserodt, Jens
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p. 428 - 435
(2008/09/17)
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- NODAPA-OH and NODAPA-(NCS)n: Synthesis, 68Ga-radiolabelling and in vitro characterisation of novel versatile bifunctional chelators for molecular imaging
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This report concerns synthesis, 68Ga-radiolabelling and stability data of 1,4,7-triazacyclononane-1,4-diacetic acid-7-p-isothio-cyanatophenyl-acetic acid (NODAPA-NCS), 1,4,7-triazacyclononane-1-acetic acid-4,7-di-p-isothiocyanatophenyl-acetic acid (NODAPA-(NCS)2) and 1,4,7-triazacyclononane-1,4-diacetic acid-7-p-hydroxyphenyl-acetic acid (NODAPA-OH), versatile bifunctional chelators with potential for molecular imaging. Protein binding and exemplified conjugation are also reported.
- Riss, Patrick J.,Kroll, Carsten,Nagel, Verena,Roesch, Frank
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scheme or table
p. 5364 - 5367
(2009/06/18)
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- Ligand and complex for catalytically bleaching a substrate
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The invention relates to ligands or complexes useful as catalysts for catalytically bleaching substrates with atmospheric oxygen, and as catalysts in the of treatment of textiles such as laundry fabrics whereby bleaching by atmospheric oxygen is catalysed after the treatment. The ligand is of the general formula: wherein R1, R2, and R3independently represent a group selected from methyl, pyridin-2-yl, quinolin-2-yl, pyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, N-methyl-amido, and N-isopropyl-amido; provided at least two of R1, R2and, R3represent a coordinating group, the ligand being selected from: 1,4-bis(pyridin-2-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(quinolin-2-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyrazol-1-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(3,5-dimethylpyrazol-1-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(N-methylimidazol-2-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4,7-tris(quinolin-2-ylmethyl)-1,4,7-triazacyclononane; 1,4-bis(N-isopropylacetamido)-7-ethyl-1,4,7-triazacyclononane; and 1,4-bis(N-methylacetamido)-7-ethyl-1,4,7-triazacyclononane.
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Page/Page column 7
(2010/01/31)
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- The recovery of a rhodium-containing catalyst by various new silica-based amine ion exchangers
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Various mono-, di-, and triamine ligands have been successfully attached to an inert silica backbone. Their efficiency in the recovery of the model catalyst RhCl3 has been thoroughly investigated. Correlation of the distribution coefficients for Rh3+ as a function of the pH with recovery experiments, shows a subtle balance between the stability of the ligand- to-metal complexes and the elution efficiency. Rhodium ion exchanger complexes with log D values above 2.5 appear to be too stable to ensure a high (> 70%) desorption. A very high desorption (> 90%) has been effected with 2 M HNO3 with ion exchangers containing monoamine ligands or sterically hindered diamine ligands. The adsorption medium appeared to be of major influence, both on the extractability and on the elution possibility.
- Kramer, Jurjen,Scholten, Arjen,Driessen, Willem L.,Reedijk, Jan
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p. 1488 - 1494
(2007/10/03)
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- Synthesis of a series of triaza-macrocyclicanes
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Condensation of the N, N′, N″-tris(p-toluenesulfonyl)diethylenetrimine-N,N″-disodium with bissulphonate esters of two-, three-, four- and six-carbon diols gives the corresponding 9-, 10-,11-, 13-membered triamine macrocycles containing N-ptoluenesulfonyl group, respectively. The p-tuluenesulfonyl groups are removed with concentrated sulfuric acid, acetic acidhydrobromic acid or LiAlH4 which give the ammonium salts of 1,4,7-triazacyclononane, 1,4,7-triazacyclodecane, 1,4,7-triazacycloundecane, 1,4,7-triazacyclotridecane, respectively. Comparison and details of the different synthetic procedures of the triamine macrocycles are described as well.
- Gao, Jinzhang,He, Hui,Zhang, Xuan,Lu, Xiaoquan,Kang, Jingwan
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p. 372 - 375
(2007/10/03)
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- Synthesis of polyazamacrocyclic compounds via modified Richman-Atkins cyclization of β-trimethylsilylethanesulfonamides
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The Richman-Atkins cyclization remains one of the most widely used methods for the preparation of macrocyclic polyamines. The use of β-trimethylsilylethanesulfonamides (SES-sulfonamides) for the preparation of polyazamacrocyclic compounds is described. This expands existing Richman-Atkins sulfonamide macrocyclization methodology, and it successfully enables preparation of labile polyaza[n](1,4)naphthalenophanes and polyaza[n](9,10)anthracenophanes, not previously available in appreciable quantities.
- Hoye,Hoye,Richman,Dantas,Lightbourne,Scott Shinneman
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p. 2722 - 2725
(2007/10/03)
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- Synthesis and characterisation of pendant-arm amino derivatives of 1,4,7-triazacyclononane and alkyl-bridged bis(1,4,7-triazacyclononane) macrocycles and complexation to Cu(II)
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The new pentadentate and bis(pentadentate) ligands 1-methyl-4,7-bis(3-aminopropyl)-1,4,7-triazacyclononane 6 and 1,2-bis[4,7-bis(3-aminopropyl)-1,4,7-triazacyclonon-1-yl]ethane 14 have been synthesised by reaction of acrylonitrile with the corresponding macrocyclic precursors and subsequent reduction of the nitrile groups with BH3*THF. Cu(II) complexes of the two ligands having formulations [Cu(6)][BF4]2 and [Cu2(14)][PF6]4*6MeCN, respectively, have been prepared and structurally characterised. Both complexes exhibit distorted square-based pyramidal geometries about the metal centres with the two primary amino groups belonging to the pendant arms occupying basal positions [Cu-Nap 2.257(6), Cu-Neq 2.026(6)-2.074(5) Angstroem for [Cu(6)]2+, and 2.337(2) and 2.038(3)-2.085(3) Angstroem for [Cu2(14)]4+]. The binuclear complex [Cu2(14)]4+ is centrosymmetric about the ethane bridge with the two pentadentate compartments oriented away from one another to give a transoid anti-configuration with a MeCN molecule interacting with each Cu(II) centre at 2.710(4) Angstroem. Both complexes have also been characterised by electronic and EPR spectroscopy and by cyclic voltammetry, and their properties compared to those of Cu(II) complexes of analogous macrocyclic ligands having 2-methylpyridyl pendant arms.
- Blake, Alexander J.,Danks, Jonathan P.,Li, Wan-Sheung,Lippolis, Vito,Schroeder, Martin
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p. 3034 - 3040
(2007/10/03)
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- Cascade polymer bound chelating compounds, their chelates and conjugates, processes for their production, and pharmaceutical agents containing them
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Cascade polymers, containing complex-forming ligands, optionally at least five ions of an element of atomic numbers 21-29, 39, 42, 44 or 57-83, as well as, if desired, cations of inorganic and/or organic bases, amino acids or amino acid amides, are valuable complexing compounds and complexes for diagnostics and therapy.
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- MACROHETEROCYCLES. 15.* SYNTHESIS OF MACROCYCLIC POLYAMINES IN A BIPHASIC SYSTEM
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Macrocyclic polyamines are conveniently synthesized by condensation of bissulfonamides with ditosylates or dibromides of glycols in the biphasic system toluene(xylene)-aqueous sodium hydroxide.
- Luk'yanenko, N. G.,Basok, S. S.,Filonova, L. K.,Kulikov, N. V.,Pastushok, V. N.
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p. 346 - 349
(2007/10/02)
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- SYNTHESIS AND COPPPER(I) COMPLEXES OF A SERIES OF 9- TO 13-MEMBERED N3 MACROCYCLES
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Eight cyclic triamines with ring sizes between 9 and 13 were synthesized by the p-toluenesulfonate method.The open-chain triamines bis(2-aminoethyl)amine (dien) and bis(3-aminopropyl)amine (diprop) were used as starting materials.In some cases, the corresponding dimeric cyclic hexaamines have been isolated and characterized as major by-products.The complexation of Cu(I) by the triamines has been studied potenciometrically in CH3CN/H2O.All ligands L form ternary complexes .The corresponding association constants vary between 1E11 and 1E7, decreasing with increasing ring size.In addition , complexes yLH>(2+), y= 1 or 2, are found as less important species with maximum concentrations of 7 to 50 percent.
- Briellmann, Markus,Kaderli, Susan,Meyer, Charles J.,Zuberbuehler, Andreas D.
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p. 680 - 689
(2007/10/02)
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