Search results for "ion chemistry"
showing 10 items of 254 documents
The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts
2005
The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…
Experimental and Theoretical Studies of Nonclassical d 0 Cyclopentadienyl Polyhydride Complexes of Molybdenum and Tungsten
1998
Low-temperature protonation of compounds Cp{sup *}MH{sub 5}(PMe{sub 3}) (M = Mo, 1; W, 2) by HBF{sub 4}{center_dot}Et{sub 2}O in CD{sub 2}Cl{sub 2} or CDFCl{sub 2} affords the thermally unstable hexahydride derivatives [Cp{sup *}MH{sub 6}(PMe{sub 3})]{sup +} (M = Mo, 3; W, 4). The corresponding protonation of 1- and 2-d{sup 5} affords 3- and 4-d{sup 5}, respectively. The {Delta}{delta} on going from H{sub 6} to HD{sub 5} is small for both compounds, but positive for 3 and negative for 4, and no isotopic perturbation of resonance (IPR) is observed. The T{sub 1min} at 400 MHz for [Cp{sup *}MH{sub 6}(PMe{sub 3})]{sup +} apparently doubles on going from Mo to W (52 ms for 3 and approximately 10…
Recent advances in electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrins
2020
Abstract Recent studies on electrochemical meso- and β-functionalization of porphyrins and electrografting of diazonium porphyrin are presented. First, the electrochemical oxidative C–C coupling between porphyrins will be presented, followed by the intermolecular and intramolecular meso- and β-substitutions of porphyrins. Then, the latest results on diazonium porphyrin electrografting will be reviewed.
Phosphine-diène and Salicylamidines ligands : coordination chemistry, catalysis and therapy
2017
The subject of this thesis concerns the development of new ligands, their coordination chemistry, and the synthesis of the corresponding metal complexes for catalysis and therapy.The first part of this work relates to the synthesis of diene-phosphine ligands, their saturated analogs, and the corresponding arene-ruthenium complexes. Arene decoordination allows the formation of a cationic bimetallic complex where the ligand is diène-η4/κ-P coordinated to the ruthenium. These complexes have been applied to atom transfer radical addition (ATRA) of CCl4 to styrene. When harsh reaction conditions are used, the superiority of the “diene” complexes is highlighted comparing to saturated analogs.The …
Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone
2021
International audience; Anionic phosphinoferrocene amidosulfonates bearing sterically demanding t-butyl substituents in positions 3 and 3' of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η5-tBuC5H3PR2)(η5-tBuC5H3C(O)NHCH2SO3)] (R = phenyl and cyclohexyl) were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η5-tBuC5H3PR2)(η5-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-t-butylated analogues have been used as lig-ands to prepare zwitterionic (η3-allyl)palladium(II) complexes [Pd(η3-C3H5){Fe(η5-R'C5H3PR2)(η5-R'C5H3C(O)NHCH2SO3)}] (R' = H, tBu, R = Ph, Cy). Depending on the isolation procedure and crystallization condi-tions, some complexes we…
Development of Polyamine‐Substituted Triphenylamine Ligands with High Affinity and Selectivity for G‐Quadruplex DNA
2019
Currently, significant efforts are devoted to designing small molecules able to bind selectively to guanine quadruplexes (G4s). These noncanonical DNA structures are implicated in various important biological processes and have been identified as potential targets for drug development. Previously, a series of triphenylamine (TPA)-based compounds, including macrocyclic polyamines, that displayed high affinity towards G4 DNA were reported. Following this initial work, herein a series of second-generation compounds, in which the central TPA has been functionalised with flexible and adaptive linear polyamines, are presented with the aim of maximising the selectivity towards G4 DNA. The acid-bas…
Imidazoporphyrins as supramolecular tectons: synthesis and self-assembly of zinc 2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrinate
2019
International audience; 5,10,15,20-Tetramesityl-2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrin (PyPor) bearing a pyridine donor site connected to the tetrapyrrolic macrocycle by a rigid imidazole linker was prepared in high yield by the condensation of the corresponding 2,3-dioxochlorin and 4-formylpyridine in the presence of ammonium acetate. After the insertion of a metal ion capable of metal–ligand axial coordination, namely Zn(II), this compound afforded self-complementary porphyrin PyPorZn which was suitable for self-assembly. In the crystals, this complex exists as a zigzag coordination polymer formed through the axial coordination of the pyridine nitrogen atom to the zinc ion of the neighb…
Coordination self-assembly through weak interactions in meso-dialkoxyphosphoryl-substituted zinc porphyrinates.
2019
International audience; The self-assembly of seven zinc 10-(dialkoxyphosphoryl)-5,15-diarylporphyrinates Zn5-Zn11 containing different substituents at the phosphonate and aryl groups was investigated. Single crystals of Zn5-Zn9 complexes were grown under the same conditions and analyzed by X-ray structural analysis. A supramolecular self-assembly is observed in all crystals through weak coordinative bonding of the phosphoryl group of one porphyrin molecule to the zinc(II) ion of a second porphyrin molecule. The geometry of the porphyrin macrocycle is similar in all of the studied crystals and the central zinc atom in each case adopts a distorted tetragonal pyramidal environment. However, th…
Biological Evaluation of the NIR-Emissive Ruby Analogue [Cr(ddpd) 2 ][BF 4 ] 3 as a Photodynamic Therapy Photosensitizer
2018
International audience; Photodynamic therapy relies on the bioavailability of photosensitizers with suitable photophysical, chemical and biochemical properties. Although the photophysical properties, stability and high water solubility of the chromium(III) complex [Cr(ddpd)2][BF4]3 (ddpd = N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine) are very favorable, its photocytotoxicity against cancerous and non-cancerous cell lines has not yet been elucidated. We now report the cytotoxicity and photocytotoxicity of the complex [Cr(ddpd)2][BF4]3 against human cervical cancer cells, human primary glioblastoma cells, human glioblastoma astrocytoma cells and non-cancerous retinal pigment epithel…
Reduction of ferricytochrome c catalyzed by optically active chromium(III) complexes
2009
The reduction rates of horse heart ferricytochrome c by amalgamated zinc or by electrolysis at fixed potential on a mercury pool as the cathode have been measured in a buffered solution at pH 7.5 by absorption spectrophotometry. In both cases, the reaction was strongly accelerated by the presence of the optically active complexes Lambda-[Cr(III)((S,S)-promp)H(2)O](+) (H(2)promp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(S)-proline]), Delta-[Cr(III)((R,R)-alamp)H(2)O](+) (H(2)alamp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(R)-alanine]) and Lambda-[Cr(III)((S,S)-alamp)(H(2)O)(2)](+). These were shown to undergo reversible one-electron reduction to the corresponding labile chromium(…