13406-27-4

Upstream product

• 13406-29-6 tris(para-trifluoromethyl)phenyl phosphine 
• 1366181-69-2 [(κ2-P,O-2-(bis(2-methoxyphenyl)phosphino)benzenesulfonato)PdMe(OP(p-CF3C6H4)3)] 
• 603-35-0 triphenylphosphine 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 13406-26-3 4-Dimethylamino-N--anilin 

Downstream Products

• 13406-29-6 tris(para-trifluoromethyl)phenyl phosphine 
• 1366181-69-2 [(κ2-P,O-2-(bis(2-methoxyphenyl)phosphino)benzenesulfonato)PdMe(OP(p-CF3C6H4)3)] 
• 15929-43-8 bis(4-(trifluoromethyl)phenyl)phosphine oxide 
• 1449430-76-5 (E)-[2-(1,2-diphenylethenyl)-4-(trifluoromethyl)phenyl]bis-[4-(trifluoromethyl)phenyl]phosphine oxide 

Relevant academic research and scientific papers

Chemistry of singlet oxygen with arylphosphines

The chemistry of singlet oxygen with a variety of arylphosphines has been studied. Rates of singlet oxygen removal by para-substituted arylphosphines show good correlation with the Hammett σ parameter (ρ=-1.53 in CDCl3), and with the Tolman electronic parameter. The only products for the reactions of these phosphines with singlet oxygen are the corresponding phosphine oxides. Conversely, for ortho-substituted phosphines with electron-donating substituents, there are two products, namely a phosphinate formed by intramolecular insertion and phosphine oxide. Kinetic analyses demonstrate that both products are formed from the same intermediate, and this allows determination of the rate ratios for the competing pathways. Increasing the steric bulk of the phosphine leads to an increase in the amount of insertion product. VT NMR experiments show that peroxidic intermediates can only be detected for very hindered and very electron-rich arylphosphines.

The Influence of Peripheral Substituent Modification on PV, MnIII, and MnV(O) Corrolazines: X-ray Crystallography, Electrochemical and Spectroscopic Properties, and HAT and OAT Reactivities

The influence of remote peripheral substitution on the physicochemical properties and reactivity of phosphorus and manganese corrolazine (Cz) complexes was examined. The substitution of p-MeO for p-t-Bu groups on the eight phenyl substituents of the β-car

The Trityl-Cation Mediated Phosphine Oxides Reduction

Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).

Mechanism of O-Atom Transfer from Nitrite: Nitric Oxide Release at Copper(II)

Nitric oxide (NO) is a key signaling molecule in health and disease. While nitrite acts as a reservoir of NO activity, mechanisms for NO release require further understanding. A series of electronically varied β-diketiminatocopper(II) nitrite complexes [CuII](κ2-O2N) react with a range of electronically tuned triarylphosphines PArZ3 that release NO with the formation of O═PArZ3. Second-order rate constants are largest for electron-poor copper(II) nitrite and electron-rich phosphine pairs. Computational analysis reveals a transition-state structure energetically matched with experimentally determined activation barriers. The production of NO follows a pathway that involves nitrite isomerization at CuII from κ2-O2N to κ1-NO2 followed by O-atom transfer (OAT) to form O═PArZ3 and [CuI]-NO that releases NO upon PArZ3 binding at CuI to form [CuI]-PArZ3. These findings illustrate important mechanistic considerations involved in NO formation from nitrite via OAT.

Photooxidation of triarylphosphines under aerobic conditions in the presence of a gold(iii) complex on cellulose extracted from Carthamus tinctorius immobilized on nanofibrous phosphosilicate

Triarylphosphines were converted to the corresponding oxides via photooxidation as a novel method. In this study, cellulose was extracted from the Carthamus tinctorius plant and then oxidized by sodium metaperiodate. A gold complex was supported on this natural cellulose. Then, a gold complex on natural cellulose supported on FPS (FPS/Au(iii)) was synthesized for the reduction of phosphine oxides to corresponding phosphines with remarkable chemoselectivity. The morphology of FPS led to higher catalytic activity. FPS/Au(iii) NPs were thoroughly characterized using TEM, FESEM, FTIR, TGA, and BET.

Ir(III)-catalyzed direct C-H functionalization of arylphosphine oxides: A strategy for MOP-type ligands synthesis

Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C-H functionalization of arylphos-phine oxides. Involving C-H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework.

Ruthenium-catalyzed ortho -alkenylation of phenylphosphine oxides through regio- and stereoselective alkyne insertion into C-H bonds

Direct ortho-substitution took place efficiently upon treatment of tri-, di-, and monoarylphosphine oxides with internal alkynes in the presence of a ruthenium catalyst to produce (o-alkenylphenyl)phosphine oxides regio- and stereoselectively. Chemoselective reduction of a product gave the corresponding (o-alkenylphenyl)phosphine, which may be useful as a ligand for transition metals.

Limits of activity: Weakly coordinating ligands in arylphosphinesulfonato palladium(II) polymerization catalysts

The coordination strength of various phosphine oxides OPR3 toward the olefin polymerization catalyst (PλO)PdMe (P λO = κ2-P,O-Ar2PC 6H4SO2O with Ar = 2-MeOC6H 4) as compared to that of dmso has been determined. Equilibrium constants KL for the reaction 1-dmso + L ? 1-L + dmso range from 3.5 for electron-rich OPBu3 to 10-3 for electron-poor OP(p-CF3C6H4)3. Complexes derived from more strongly coordinating phosphine oxides, i.e. [(PλO) PdMe(L)] (1-L; L = OPBu3, OPOct3, OPPh3) have been isolated and fully characterized. Additionally, 1-OPBu3 and 1-OPPh3 were analyzed by X-ray diffraction analyses. Complexes derived from weakly coordinating phosphine oxides have eluded isolation due to loss of phosphine oxide and formation of barely soluble multinuclear palladium complexes 1n by bridging coordination of the sulfonate group to various Pd centers. Hence, the (PλO)PdMe fragment 1 exhibits an intrinsic limitation with respect to coordination of weak donors. Species 1 generated in situ in the absence of additional ligand (L) has been identified in homo- and copolymerization experiments as well as NMR insertion studies as the most active possible catalyst. Since 1 is generated from the easily available precursor [{(1-Cl)-ν-Na}2)], these findings give rapid access to highly active (PλO)PdMe catalysts.

Reduction of tertiary phosphine oxides with DIBAL-H

(Chemical Equation Presented) The reduction of tertiary phosphine oxides (TPOs) and sulfides with diisobutylaluminum hydride (DIBAL-II) has been studied in detail. An extensive solvent screen has revealed that hindered aliphatic ethers, such as MTBE, are optimum for this reaction at ambient temperature. Many TPOs undergo considerable reduction at ambient temperature and then stall due to inhibition. 31P and 13C NMR studies using isotopically labeled substrates as well as competition studies have revealed that the source of this inhibition is tetraisobutyldialuminoxane (TIBAO), which builds up as the reaction proceeds. TIBAO selectively coordinates the TPO starting material, preventing further reduction. Several strategies have been found to circumvent this inhibition and obtain full conversion with this extremely inexpensive reducing agent for the first time. Practical reduction protocols for these critical targets have been developed.

Synthesis of cationic rhenium(VII) oxo imido complexes and their tunability towards oxygen atom transfer

A facile method is described for the synthesis of cationic Re(VII) cis oxo imido complexes of the form [Re(O)(NAr)(salpd)+] (salpd = N,N′-propane-1,3-diylbis(salicylideneimine)), 4, [Re(O)(NAr)(saldach) +] (saldach = N,N′-cyclohexane-1,3-diylbis(salicylideneimine)), 5, and [Re(O)(NAr)(hoz)2+] (hoz = 2-(2′- hydroxyphenyl)-2-oxazoline) (Ar = 2,4,6,-(Me)C6H2; 4-(CF3)C6H4; 4-(Me)C6H4; 4-(CF3)C6H4; 4-MeC6H 4SO2), 6, from the reaction of oxorhenium(V) [(L)Re(O)(Solv)+] (1-3) and aryl azides under ambient conditions. Unlike previously reported cationic Re(VII) dioxo complexes, these cationic oxo imido complexes can be obtained on a preparative scale, and an X-ray crystal structure of [Re(O)(NMes)(saldach)+], 5a, has been obtained. Despite the multiple stereoisomers that could arise from tetradentate ligation of salen ligands to rhenium, one major isomer is observed and isolated in each instant. The electronic rationalization for stereoselectivity is discussed. Investigation of the mechanism suggests that the reactions of Re(V) with aryl azides proceed through an azido adduct similar to the group 5 complexes of Bergman and Cummins. Treatment of the cationic oxo imido complexes with a reductant (PAr 3, PhSMe, or PhSH) results in oxygen atom transfer (OAT) and the formation of cationic Re(V) imido complexes. [(salpd)Re(NMes)(PPh 3)+] (7) and [(hoz)2Re(NAr)(PPh 3)+] (Ar = m-OMe phenyl) (9) have been isolated on a preparative scale and fully characterized including an X-ray single-crystal structure of 7. The kinetics of OAT, monitored by stopped-flow spectroscopy, has revealed rate saturation for substrate dependences. The different plateau values for different oxygen acceptors (Y) provide direct support for a previously suggested mechanism in which the reductant forms a prior-equilibrium adduct with the rhenium oxo (ReVII = O←Y). The second-order rate constants of OAT, which span more than 3 orders of magnitude for a given substrate, are significantly affected by the electronics of the imido ancillary ligand with electron-withdrawing imidos being most effective. However, the rate constant for the most active oxo imido rhenium(VII) is 2 orders of magnitude slower than that observed for the known cationic dioxo Re(VII) [(hoz) 2Re(O)2+].