- THE ANODIC TETRAMERIZATION OF THE N-BENZYLAZIRIDINE : A CHAIN PROCESS
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Benzylaziridine is oxidized anodically in organic solvents.The tetramer (tetra-aza-cyclododecane) is obtained in good yield and the electrical consumption is very low.Authors propose a chain process mechanism in comparison with the chemical method.
- Kossai, Ridha,Simonet, Jacques,Dauphin, Gerard
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- Enhancement of electrocatalytic abilities toward CO2reduction by tethering redox-active metal complexes to the active site
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Tethering metal complexes, like [Ru(bpy)2Cl2] (bpy = 2,2′-bipyridine), which are redox-active at low reduction potentials and have the ability to transfer electrons to another complex, to a [Ni(cyclen)]2+electrocatalyst enhanced the reduction of CO2to CO at low overpotentials. The [Ni(cyclen)]2+electrocatalyst was modified by tethering redox-active metal complexesvia4-methylpyridyl linkers. The redox-active metal complexes were reduced after CO2bound to the active site. In controlled potential electrolysis (CPE) experiments in 95?:?5 (v/v) CH3CN/H2O, [{([Ru]pic)4cyclen}NiCl]5+([Ru]+= {Ru(bpy)2Cl}+; pic = 4-methylpyridyl) could be used to reduce CO2into CO at a turnover frequency (TOF) of 708 s?1with a faradaic efficiency (FE) of 80% at an onset potential of ?1.60 Vvs. NHE. At the same time, this electrocatalyst was active at an onset potential of ?1.25 Vvs. NHE, which is the reduction potential of one of the bpy ligands of the [Ru]+moieties, with FE = 84% and TOF = 178 s?1. When the electrocatalysis was performed using [bn4cyclenNiCl]Cl (bn = benzyl) without tethered redox-active metal complexes, the TOF value was determined to be 8 s?1with FE = 77% at an onset potential of ?1.45 Vvs. NHE. The results show that tethering redox-active metal complexes significantly improves the electrocatalytic activities by lowering the potential needed to reduce CO2
- Breedlove, Brian K.,Cosquer, Goulven,Md. Ahsan, Habib,Yamashita, Masahiro
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- Tetrabenzylcyclen as a receptor for fluoride
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A tetraazacyclic ligand, tetrabenzylcyclen (L), was synthesized using an improved method with a higher yield by treatment of cyclen with benzylchloride in the presence of potassium carbonate. The reaction of L with an aqueous solution of fluorosilicic aci
- Gelmboldt, Vladimir O.,Ganin, Eduard V.,Basok, Stepan S.,Kulygina, Ekaterina Yu.,Botoshansky, Mark M.,Kravtsov, Victor Ch.,Fonari, Marina S.
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- From Cyclic Peptoids to Peraza-macrocycles: A General Reductive Approach
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Peraza-macrocycles form chelates of high thermodynamic and kinetic stability useful in diagnostic imaging (MRI, SPECT, PET), in coordination chemistry, and as catalysts. In this letter, we report an advantageous method to prepare these compounds via BHsu
- Schettini, Rosaria,D'Amato, Assunta,Pierri, Giovanni,Tedesco, Consiglia,Della Sala, Giorgio,Motta, Oriana,Izzo, Irene,De Riccardis, Francesco
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p. 7365 - 7369
(2019/10/02)
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- A direct method for the N-tetraalkylation of azamacrocycles
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An efficient protocol for the direct synthesis of N-tetraalkylated derivatives of the azamacrocycles cyclam and cyclen has been developed, using a partially miscible aqueous-organic solvent system with propargyl bromide, benzyl bromide, and related halide
- Counsell, Andrew J.,Jones, Angus T.,Todd, Matthew H.,Rutledge, Peter J.
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p. 2457 - 2461
(2016/12/09)
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- Argentivorous molecules: Structural evidence for Ag+-π interactions in solution
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Tetra-armed cyclens bearing aromatic side arms were prepared by the reductive amination of cyclen with substituted benzaldehydes. When equimolar amounts of Ag+ ions were added to the ligands, the aromatic rings covered the Ag+ ions i
- Habata, Yoichi,Ikeda, Mari,Yamada, Sachiko,Takahashi, Hiroki,Ueno, Sumiko,Suzuki, Takatoshi,Kuwahara, Shunsuke
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supporting information
p. 4576 - 4579
(2012/10/29)
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- Oxidation of N-benzyl aziridine by molecular iodine: Competition of electron transfer and heterolytic pathways
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Excess N-benzyl aziridine (1) reacts with I2 to afford dimer 2, tetramer 3, benzaldehyde (4), and iodoamine 5. The reaction is interpreted as occurring by both electron transfer (ET) and heterolytic mechanisms. An ET mechanism is substantiated
- Caproiu, Miron,Florea, Cristina,Galli, Carlo,Petride, Aurica,Petride, Horia
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p. 1037 - 1043
(2007/10/03)
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- The oxidation of N-benzylaziridine catalyzed by iron porphyrin: Radical versus electron transfer mechanism
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A change in the mechanism of biomimetic oxidation of tertiary amines in response to appropriate structural features of the substrate, emerges from the investigation of the product pattern from N-benzylaziridine under bona fide radical or electron transfer conditions. This substrate is an amine endowed with a high oxidation potential as a result of steric constraint. Consequently, the hydrogen atom transfer route of oxidative N-dealkylation competes favorably with the electron transfer route, which is the mechanism observed for the reaction of conventional tertiary amines with metalloporphyrins and oxygen donors.
- Cuppoletti, Andrea,Dagostin, Claudio,Florea, Cristina,Galli, Carlo,Gentili, Patrizia,Lanzalunga, Osvaldo,Petride, Aurica,Petride, Horia
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p. 2993 - 2999
(2007/10/03)
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- Artificial Transport of Amino-acid, Oligopeptide, and Related Anions by Macrocyclic Polyamine-Transition Metal Complex Carriers
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Transition-metal complexes of the macrocylic polyamine, 1,4,7,10-tetrabenzyl-1,4,7,10-tetra-azacyclododecane have been shown to be new and powerful 'metallo-carriers' for the transport of amino-acid and oligopeptide derivatives.Their transport properties are generally different from previously reported systems, and are essentially controlled by factors such as the nature of the central metal ion, and the antiport anion.The metallo-carriers described provide both a successful example of artificial oligopeptide transport, and a unique and interesting transport phenomenon across a chloroform liquid membrane.
- Tsukube, Hiroshi
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