238403-27-5Relevant academic research and scientific papers
Variable-temperature NMR studies of soluble polymer-supported phosphine-silver complexes
Bergbreiter, David E.,Yang, Yun-Chin
, p. 873 - 878 (2010)
(Chemical Equation Presented) The use of polymers as supports for organometallic catalysts has received wide attention. However, catalyst reactivity is sometimes altered as a consequence of catalyst immobilization by a polymeric ligand and such altered reactivity can complicate such supported catalysts' use. The results in this study show that heptane phase selectively soluble polyisobutylene (PIB)-bound phosphine ligands have essentially identical kinetic behavior when compared to electronically similar isobutyldiphenylphosphine analogues in phosphine coordination and exchange in silver(I) halide complexes. These studies used variable-temperature 31P NMR spectroscopy to probe the silver-phosphine exchange processes for both AgI and AgCl complexes of these polymeric and low molecular weight phosphine ligands. The results show that the dynamic behavior of the PIB- and isobutyldiphenylphosphine-AgX complexes is nearly identical based on line-shape analysis of these 31P NMR spectra as a function of temperature. Similar studies of more polar poly(ethylene glycol)triarylphosphine-bound AgX complexes and electronically analogous low molecular weight AgX complexes have similar behavior in variable-temperature 31P NMR spectroscopy.
Nanotube composites consisting of metal nanoparticles and polythiophene from electropolymerization of terthiophene-functionalized metal (Au, Pd) nanoparticles
Umeda, Ryuhei,Awaji, Hiroshi,Nakahodo, Tsukasa,Fujihara, Hisashi
, p. 3240 - 3241 (2008)
We have developed a new method for the fabrication of metal nanoparticle/polythiophene nanotube composites, i.e., the template-based electrochemical polymerization of terthiophene-linked oligoethyleneoxy-thiol (1) and -phosphine (2)-stabilized gold and pa
A general strategy to add diversity to ruthenium arene complexes with bioactive organic compounds: Via a coordinated (4-hydroxyphenyl)diphenylphosphine ligand
Biancalana, Lorenzo,Batchelor, Lucinda K.,De Palo, Alice,Zacchini, Stefano,Pampaloni, Guido,Dyson, Paul J.,Marchetti, Fabio
, p. 12001 - 12004 (2017/09/25)
Esterification of (4-hydroxyphenyl)diphenylphosphine, coordinated to the [Ru(η6-p-cymene)Cl2] fragment, allows a series of bioactive carboxylic acids to be introduced directly into the organometallic molecule. Evaluation of the compounds on human ovarian cancer cells reveals synergistic enhancements in their antiproliferative activity relative to their bioactive organic and organometallic precursors.
Recycling Pd colloidal catalysts using polymeric phosphine ligands and polyethylene as a solvent
Priyadarshani, Nilusha,Suriboot, Jakkrit,Bergbreiter, David E.
, p. 1361 - 1367 (2013/06/27)
Polyisobutylene (PIB)-bound azo dyes were prepared from aryl amine terminated polyisobutylene oligomers and used to form palladacycle precatalysts that can be used for catalytic carbon-carbon cross coupling reactions. The catalysts so formed were recyclable using thermomorphic heptane-DMF solutions that are monophasic at 80 °C and biphasic at room temperature. Under these conditions, the Pd catalyst can be recycled but some Pd leaches into the product solution. Using a low melting polyethylene oligomer as a solvent in place of the volatile heptane solvent reduces this leaching by roughly an order of magnitude. Further modification that involves using a second polyisobutylene (PIB)-bound phosphine ligand both increases the activity of the colloidal Pd catalyst and decreases the total Pd leaching by almost two orders of magnitude with 99.88% of the Pd being recovered. In this case, the Pd content in the solution of the product was ca. 0.3 ppm. These two modifications together lead to a much more sustainable strategy for the use of Pd colloidal catalysts in catalytic cross coupling chemistry.
Enhanced catalytic activity in suzuki-miyaura couplings by shell crosslinked pd nanoparticles from alkene-terminated phosphine dendron-stabilized Pd nanoparticles
Shiomi, Toshiaki,Nakahodo, Tsukasa,Fujihara, Hisashi
, p. 1700 - 1702 (2013/02/23)
New alkene-terminated phosphine dendron-protected palladium nanoparticles (NPs) have been synthesized, and the olefin metathesis polymerization of their Pd NPs led to shell crosslinked Pd NPs without aggregation of the Pd NPs. The introduction of crosslinking at the surface of the protective ligand enhanced the catalytic activity of the Pd NPs for SuzukiMiyaura couplings.
Low molecular weight MPEG-assisted organic synthesis
Figlus, Marek,Tarruella, Albert C.,Messer, Anastasia,Sollis, Steven L.,Hartley, Richard C.
supporting information; experimental part, p. 4405 - 4407 (2010/09/15)
A toolkit of low molecular weight MPEG-supported coupling agents ( MIIDQ, MEDCI), reagents for the Mitsunobu reaction ( MDEAD, MTPP), an alternative to diazomethane, and scavengers can be used in the solution-phase synthesis of amides, esters and ureas and are easily removed after use by solid-phase extraction (MSPE) using normal silica.
Exploiting poly(ethylene glycol) as a matrix for liquid-phase organic synthesis
Sieber, Frank,Wentworth Jr., Paul,Janda, Kim D.
, p. 1018 - 1032 (2007/10/03)
Soluble polymer-supported chemistry is a technology that allows the blending of the benefits of polymer-supported synthesis and solution-phase chemistry. Herein, we describe our recent efforts in this area targeted at exploring the scope of poly(ethylene glycol) (PEG) as the matrix. Specifically we describe the use of PEG as a support for triphenyl phosphine and for the Stille reaction.
Development and Application of a Poly(ethylene glycol)-Supported Triarylphosphine Reagent: Expanding the Sphere of Liquid-Phase Organic Synthesis
Sieber, Frank,Wentworth Jr., Paul,Toker, Jonathan D.,Wentworth, Anita D.,Metz, William A.,Reed, Neal N.,Janda, Kim D.
, p. 5188 - 5192 (2007/10/03)
Continuing studies into the utility of poly(ethylene glycol) (PEG)-supported triarylphosphines as functional polymer reagents in liquid-phase organic synthesis (LPOS) are being pursued. This report describes the synthesis and NMR characterization of an aryl-alkyl ether-linked PEG-triarylphosphine derivative (2) and its subsequent application in LPOS. The utility of 2 as a mild stoichiometric reagent for ozonide reduction has been demonstrated, and a direct comparison between 2, a Merrifield resin-bound triarylphosphine derivative, and a solution-phase triphenylphosphine reagent revealed that the highest observed yields occur under liquid-phase conditions. Transformation of phosphine 2 into a phosphonium salt (3) then allowed the inherent aqueous solubility of PEG-functionalized moieties to be exploited by enabling a Wittig reaction, between a range of aldehydes and 3, to occur under mildly basic aqueous conditions. This led to the generation of substituted stilbenes in good to excellent yields. Finally, regeneration of 2 was achieved by reduction of the PEG-supported triphenylphosphine oxide byproduct 4 with alane (100% conversion, 75% yield). This combination of reaction, recovery, and regeneration expands the utility of PEG-supported triarylphosphine reagents across the spectra of both organic chemistry and solution-phase combinatorial strategies.
