μ‐Phthalocyaninato‐bis(triphenylphosphinoxidnatrium): Synthese und Kristallstruktur

μ‐Phthalocyaninato‐bis({triphenylphosphine oxide}sodium): Synthesis and Crystal Structure Blue μ‐phthalocyaninato‐bis({triphenylphosphine oxide}sodium) ( 1 ) is prepared by heating triphenylphosphine oxide with disodium phthalocyaninate at 160 °C. 1 is centrosymmetric (space group P1). The Na atom is located in a tetragonal pyramid co‐ordinating four isoindole N atoms at a distance varying between 2.409(2) and 2.438(2) Å, and one O atom at 2.198(2) Å. The Na–Na distance is 2.823(5) Å, and the Na–O–P angle is 145.5(1)°.     

伯胺N1923和三苯基氧化膦萃取金(Ⅲ)的动力学Ⅱ:二元萃取剂体系萃取AuCl4-

用恒界面池法研究了伯胺N1923和三苯基氧化膦(TPPO)二元萃取剂体系从盐酸介质中萃取AuCl4-的动力学,提出了界面化学反应控制机理.认为在界面区域内同时进行着N1923、TPPO以及二者的缔合物萃取AuCl4-的三个平行反应.三者的共同作用使Au(Ⅲ)向有机相的传质较N1923或TPPO的一元萃取剂体系明显加速.文中对这种动力学加速现象和动力学协同效应以及它们与热力学协同萃取的关系进行了讨论.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Reaction of triphenylphosphine with poly(ethylene terephthalate) and certain model compounds at elevated temperature

Triphenylphosphine and poly(ethylene terephthalate) react at 370°C to produce ethylene, triphenylphosphine oxide, carbon dioxide, benzoic acid, and terephthalic acid. The reaction proceeds by the initial formation of a zwitterionic species which then generates a phosphonium ylid and leads to the observed products. Any flame retardant activity from the use of triphenyl-phosphine may be attributed to the formation of triphenylphosphine oxide. The co-production of ethylene renders triphenylphosphine a less effective flame retardant than triphenylphosphine oxide.     

Controlling/living polymerization of MMA with RGO/BiVO4 as photoinitiator

In this study, reduced grapheme oxide (RGO)/BiVO₄ composite was prepared and characterized by FT-IR, XRD, and UV spectrum. Photo-chemically-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully performed at 25°C in N,N-dimethylformamide (DMF) with RGO/BiVO₄ as photoinitiator, FeCl₃·6H₂O/triphenylphosphine (PPh₃) as catalyst, and ethyl 2-bromoisobutyrate as ATRP initiator. MMAs were polymerized in a controlled manner under ultraviolet (UV) light and sunlight conditions. The results show that a first-order kinetics model was obeyed up to higher conversion. The reaction gave well-controlled PMMA with M_n,GPC close to the theoretical value and a narrow MWD (M_w/M_n<1.5). The experiments of light on and off reveal the photoredox cycle between Fe(III) and Fe(II) species. The living character was further verified by the chain extension experiments.     

Graphene oxide dispersions in organic solvents

The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.     

Adduct of Triphenylphosphine Oxide and Sulfuric Acid: Synthesis and Structure

Adduct of triphenylphosphine oxide and sulfuric acid was synthesized by reacting arenesulfonic acids with triphenylphosphine oxide (1 : 2) in the presence of the moisture of air. According to the X-ray diffraction data, the phosphorous atom has a distorted tetrahedral coordination. The sulfuric acid molecule is disordered over two sites and is linked with two triphenylphosphine oxide molecules through hydrogen bonds.     

Configurationally stable propeller-like triarylphosphine and triarylphosphine oxide

Configurationally stable, propeller-like triarylphosphine and triarylphosphine oxide can be synthesized; a chiral scaffold based on Lissoclinum-cyclopeptides linked via three peptide bonds with a triphenylphosphine and triphenylphosphine oxide moiety, respectively, prevents effectively epimerization at the chiral phosphorus atom.     

The preparation and tin-119 Mössbauer spectra of new adducts of the type organotetrachlorostannate(IV) base (11)

New adducts Et₄N(RSnCl₄ · L) (R butyl and phenyl; L pyridine, trimethylamine, tri-n-butylphosphine, triphenylphosphine oxide, triphenylarsine oxide, dimethylsulphoxide, dimethylformamide) have been isolated and their Mössbauer spectra studied. Definite structural assignments are made for the phosphine and phosphine oxide adducts from Mössbauer quadrupole splitting data. Comments are made on the choice of partial splitting values for phenyl and butyl groups.     

A novel tetrakis(pyrazolyl)borate ligand bearing triphenylphosphine oxide substituents

A new tetrakis(pyrazolyl)borate ligand bearing triphenylphosphine oxide moieties appended to the 3-position of the pyrazolyl rings is reported and shown to display varied coordination chemistry from tridentate N(2)O coordination with thallium to hexadentate N(3)O(3) coordination with europium.     

Lithium chloride-induced organogel transformed from precipitate based on cyclodextrin complexes

This paper describes a novel heat-set organogel transformation which could be triggered by lithium chloride (LiCl) from precipitate for the first time. The system was prepared with β-cyclodextrin (β-CD) and triphenylphosphine (Ph₃P) in N,N-dimethylformamide (DMF). The system as an original transparent solution at room temperature could turn into precipitation by heating. Subsequently, the precipitation turned into organogel instantly based on the injection of LiCl into the system. SEM measurement revealed that the precipitate and gel systems have different microstructures. IR and XRD measurements revealed that the inclusion complexes formed by β-CDs and Ph₃P were arranged in cage structures in the precipitate and channel structures in the gel. Molecular dynamics simulations were performed both on the formation of the precipitate and gel models in this system, which were consistent with the test results.     

Efficient scavenging of Ph3P and Ph3P=O with high-loading merrifield resin

[see reaction]. A simple, highly effective method for removing triphenylphosphine and/or triphenylphosphine oxide from reaction mixtures is described. Commercially available high-loading chloromethylated polystyrene 1, modified in situ with NaI, acts as a scavenger resin. Several coupling reactions catalyzed by Pd(0) or Ni(0) which require the removal of triphenylphosphine are tested.     

Electroreduction of triphenylphosphine dichloride and the efficient one-pot reductive conversion of phosphine oxide to triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode. Further, the one-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide in acetonitrile with oxalyl chloride and subsequent electrochemical reduction.     

Solvation dynamics of formamide and N,N-dimethylformamide in aerosol OT reverse micelles

The solvation dynamics of formamide and N,N-dimethylformamide in Aerosol OT reverse micelles has been investigated in this work. The solvation dynamics of formamide and N,N-dimethylformamide in the reverse micelles is more than 100 times slower than that of the pure solvents. The solvation dynamics of formamide in the reverse micelle solution depends strongly on the molar ratio between formamide and Aerosol OT (w = [polar solvent]/[Aerosol OT]), but that of N,N-dimethylformamide in the reverse micelle solution shows a tiny w dependence. We have estimated the interaction energies of the geometry-optimized clusters of a simple model of the Aerosol OT polar headgroup (CH3SO3-) and formamide or N,N-dimethylformamide by ab initio calculations (the second-order M?ller-Plesset perturbation theory) to find their interactions. The interaction energies of the mimic clusters estimated by the ab initio calculations and the features of the slow solvation dynamics and w dependence in formamide and N,N-dimethylformamide reverse micelles are discussed.     

Mechanism for NO2 charging on metal supported MgO

NO2 adsorbed on MgO(100) supported by Ag or Pt is explored by density functional theory calculations. NO2 is weakly adsorbed on MgO(100), with a bond involving minor oxide to adsorbate charge transfer. However, if MgO is supported, then the adsorption energy is considerably enhanced and NO2 is adsorbed as a nitrite (N). Analysis reveals that the NO2 excess charge originates from the oxide side of the oxide/metal interface and that the electron abstraction increases the oxide/metal adhesion. The proposed mechanism is general and should apply for oxidizing surface species.     

Hysteretic sorption of light gases by a porous metal-organic framework containing tris(para-carboxylated) triphenylphosphine oxide

The porous metal-organic framework (MOF) PCM-4, based on tris(para-carboxylated) triphenylphosphine oxide, contains atypical, polar organic substituents; the material exhibits a hysteretic sorption of Ar, N2 and O2, and demonstrates the advantage of ligands of this type.     

Origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate—application of the 18O isotope effect in 31P NMR

Potassium persulfate oxidizes triphenylphosphine to triphenylphosphine oxide in 60% aqueous acetonitrile. It has been suggested that the oxygen of the product, triphenylphosphine oxide, might originate from solvent water, following nucleophilic attack on an intermediate phosphonium ion. We have investigated the origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate in 60% aqueous acetonitrile containing 20% [¹⁸O]water. The product was analyzed by using the ¹⁸O isotope effect in ³¹P NMR spectroscopy. The magnitude of the ¹⁸O isotope-induced shift was determined by synthesizing triphenylphosphine [¹⁸O]oxide and was found to be 0.038 ppm upfield. The product of the oxidation reaction in 20% [¹⁸O]water displayed no ¹⁸O isotope effect. The origin of the oxygen in the oxidation reaction is the persulfate ion, consistent with an alternative mechanism involving nucleophilic attack by water at the sulfur atom of a phosphonium peroxysulfate intermediate.     

Investigation of salt — Mixed solvent systems. XXXVII. Crystallization enthalpy of lithium chloride in mixed solvent systems

The crystallization enthalpy of LiCl at 25°C in LiCl-H₂O-cosolvent systems is determined calorimetrically as a function of the cosolvent content in the mixed solvent. This parameter is used for the investigation of heat phenomena accompanying the solvation of the salt in a saturated solution. The cosolvents employed include methanol, acetone, and N,N-dimethylformamide. The most pronounced change is effected by replacement of water with N,N-dimethylformamide.     

The recovery of gallic acid with triphenylphosphine oxide in different kind of solvents

In this study, gallic acid was separated by triphenylphosphine oxide in the presence of conventional solvents. Triphenylphosphine oxide is an organophosphorus extractant and highly selective towards carboxylic acids. Reactive extraction results were compared with physical extraction results. The extraction efficiencies reached up to 61, 76, 86, 67, and 84% in the presence of triphenylphosphine oxide with oleyl alcohol, dimethyl adipate, isobutanol, methyl isopropyl ketone, and methyl ethyl ketone, respectively. Further, the number of theoretical units and the solvent to feed ratio were calculated for the practical design of a liquid-liquid extraction column. Roughly 2 to 4 theoretical units were calculated to meet the targeted extraction efficiencies. This study is the first to investigate the reactive extraction of gallic acid by triphenylphosphine oxide, and include fundamental information for the recovery of gallic acid.     

One-pot solid phase synthesis of (E)-nitroalkenes

An efficient one-pot protocol for the synthesis of (E)-nitroalkenes by reaction of aldehydes and nitroalkanes in the presence of polymer-bound triphenylphosphine, iodine and imidazole is described. Although the reaction works with similar efficiency with triphenylphosphine and its polymer-bound version, easy removal of the unwanted polymer-bound triphenylphosphine oxide and its recovery as triphenylphosphine provide the edge for practical application of the method.