Search results for "phosphine"
showing 10 items of 618 documents
Phosphororganische Verbindungen, 85. Kinetische Untersuchungen der Umsetzung organischer Phosphorverbindungen mit Nucleophilen und Supernucleophilen
1977
Bei der alkalischen Spaltung von quartaren Phosphoniumsalzen und tertiaren Phosphinoxiden zeigt HOO⊖ keinen α-Effekt. Die Spaltung der P–C-Bindung wird auch nicht durch Gruppen erleichtert, welche uber die Ausbildung von H-Brucken den Angriff von HOO⊖ am Phosphoniumzentrum fordern. — In Ubereinstimmung mit den Ergebnissen anderer Autoren wird bei der Hydrolyse der Phosphin-, Phosphon- und Phosphorsaureester 1, 2 und 3 in Gegenwart von H2O2 ein α-Effekt beobachtet, der sich in einer Hydrolysebeschleunigung um einen Faktor von ca. 100 ausdruckt. Die Hydrolysegeschwindigkeit nimmt sowohl mit HO⊖ als auch mit HOO⊖ entsprechend folgender Reihenfolge ab: Diphenylphosphinsaure-(p-nitrophenyl)ester…
BODIPY - phosphane - gold complexes : towards the elaboration of optical theranostics
2015
This work describes new anticancer agents that could be detected by optical imaging, namely optical theranostics.After a first chapter describing the context of cancer imaging and therapy, a second chapter describes a first series of BODIPY-phosphine-gold theranostics, the synthesis of which has been optimized (less steps, shortening the reaction time, scale up). Their conjugation with biomolecules (glucose, peptide) has been achieved by developing a simple and efficient method that leads to the coupling between the gold atom of the probe and the thiol of the biomolecule (modified or not), leading to a gold sulfur bound. Hence, it makes the biovectorization of the probes possible in order t…
Synthesis of ortho-fonctionnalized arylphosphines and their applications
2020
This thesis reports with the synthesis of ortho-functionnalized phosphines bearing phosphonium and 1,2,3-triazole moieties.The synthesis of phosphines-phosphoniums, using as key-step Phospha-Fries rearrangement and Appel reaction is described. Eight new phosphines- phosphoniums, bearing aryl, alkyl or ferrocenyl fragments on the phosphonium part, have been prepared with overall yields reaching 48%. These phosphines- phosphoniums have been used in the preparation of gold (I) complexes which have been characterized using spectroscopic methods and X ray diffraction. Both gold (I) complexes and phosphines-phosphoniums have been studied in biology and these compounds turned out to be cytotoxic i…
Highly Photoluminescent Blue Ionic Platinum-Based Emitters
2019
New cycloplatinated N-heterocyclic carbene (NHC) compounds with chelate diphosphines (P^P) as ancillary ligands: [Pt(R-C^C*)(P^P)]PF6 (R = H, P^P = dppm (1A), dppe (2A), dppbz (3A); R = CN, P^P = dppm (1B), dppe (2B), dppbz (3B)) have been prepared from the corresponding starting material [{Pt(R-C^C*)(μ-Cl)}2] (R = H, A, R = CN, B) and fully characterized. The new compound A has been prepared by a stepwise protocol. The photophysical properties of 1A–3A and 1B–3B have been widely studied and supported by the time-dependent-density functional theory. These compounds show an efficient blue (dppe, dppbz) or cyan (dppm) emission in PMMA films (5 wt %), with photoluminescence quantum yield (PLQY…
Photochemical intermediates of trans-Rh(CO)L2Cl where L=PMe3, PBu3, and i-Pr2HN and cis-Rh(CO)2(i-Pr2HN)Cl in frozen organic glasses
2002
International audience; The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2(i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr>400 nm) and 2 (350<λirr<400 nm) give new species, A, with carbonyl stretching bands slightly below the parent bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be conver…
Chimie de coordination du phosphore aux métaux du groupe 11 : progrès en catalyse de couplage C-N au Cu(I) et nouveaux complexes polyphosphines de l'…
2014
Nowadays, sustainable development encourages chemists to develop new economic and ecologic synthesis, because natural ressources are reducing. Most exploited ressources are gas and petroleum, but precious metals are also essential. This thesis is focusing on the enhancement of gold and copper complexes, obtained in our laboratory from phosphorous-based ligands. In the first part, we will develop a new system for the N-arylation of pyrazoles from a copper complexe coordinated by a new hybrid phosphinoalkene ligand. In the second part, coordination properties of gold to different ferrocenic polyphosphine will be studied. Several new innovative complexes will be isolated, and could be used in …
Interesting synthetic routes from the reinvestigation of the reaction of the M(CO)6 (M=Cr, Mo and W) species with KOH
1989
Reinvestigation of the reaction of M(CO)6 (M=Cr, Mo or W) with KOH has been found to provide a very convenient route to the K[M2H(CO)10] compounds (M=Cr, Mo or W). The reaction involving Cr(CO)6 yields new potassium derivatives containing [Cr2(CO)10]2− and [HCr(CO)5]− species; also K[Cr2D(CO)10] is produced from the Cr(CO)6/KOD interaction in C2D5OD. The reaction involving two different group 6 metal carbonyls yields [MM′(CO)10(μ-H)]− (MM′=CrMo, CrW or WMo) species as their K+ and PPN+ [bis(triphenylphosphine)iminium] salts.
Suzuki-Miyaura cross-coupling of arenediazonium salts catalyzed by alginate/gellan-stabilized palladium nanoparticles under aerobic conditions in wat…
2012
The use of palladium nanoparticles stabilized by natural. beads made of an alginate/gellan mixture in the Suzuki-Miyaura cross-coupling reaction of arenediazonium. tetrafluoroborates with potassium aryltrifluoroborates. (1 : 1 molar ratio) with loading as low as 0.01–0.002. mol% under aerobic, phosphine-, and base-free conditions. in water is described. The catalyst system can be reused. several times without significant loss of activity.
A Study of the Separation of 1-Dodecene and 1-Tetradecene Hydroformylation Products in Aqueous Medium
2009
Abstract Experimental results of the solubilization of olefins in hydroformylation model systems, comprising 1-dodecene and 1-tridecanal or 1-tetradecene and 1-pentadecanal, water, butanol, sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and/or tri(m-sulfofenyl)phosphine trisodium salt (TPPTS-Na) are presented. The selected systems were used for the hydroformylation of 1-dodecene and 1-tetradecene whereby high yields of aldehydes were obtained. After the reaction, the mixture spontaneously separated into an organic phase with the reaction products and an aqueous phase comprising the catalyst and excess phosphine ligand.
Sulfonation of Triphenylphosphines and Separation of Sulfonated Triphenylphosphines by Crystallization and Solvent Extraction
2007
Abstract The effect of sulfonation conditions on the formation of sulfonated triphenylphosphines and their separation from the post‐reaction mixture, containing concentrated sulphuric acid, was studied. The solvent extraction was found to be a suitable technique to separate sulfonated triphenylphosphines from concentrated sulphuric acid, and the purity and yield was higher than obtained by crystallization from various solvents. Tributyl phosphate was a suitable extractant. Sodium salts of sulfonated triphenylphosphines could then be recovered as precipitates by treating the organic phase with the sodium hydroxide solution and separation by crystallization. The solvent extraction simplified …