Phosphine‐Initiated Cation Exchange for Precisely Tailoring Composition and Properties of Semiconductor Nanostructures: Old Concept,New Applications

Phosphine‐initiated cation exchange is a well‐known inorganic chemistry reaction. In this work, different phosphines have been used to modulate the thermodynamic and kinetic parameters of the cation exchange reaction to synthesize complex semiconductor nanostructures. Besides preserving the original shape and size, phosphine‐initiated cation exchange reactions show potential to precisely tune the crystallinity and composition of metal/semiconductor core–shell and doped nanocrystals. Furthermore, systematic studies on different phosphines and on the elementary reaction mechanisms have been performed.     

In‐Situ Microfluidic Study of Biphasic Nanocrystal Ligand‐Exchange Reactions Using an Oscillatory Flow Reactor

Oscillatory flow reactors provide a surface energy‐driven approach for automatically screening reaction conditions and studying reaction mechanisms of biphasic nanocrystal ligand‐exchange reactions. Sulfide and cysteine ligand‐exchange reactions with as‐synthesized CdSe quantum dots (QDs) are chosen as two model reactions. Different reaction variables including the new‐ligand‐to‐QD ratio, the size of the particles, and the original ligand type are examined systematically. Based on the in situ‐obtained UV/Vis absorption spectra during the reaction, we propose two different exchange pathways for the sulfide exchange reaction.     

Nanojunction‐Mediated Photocatalytic Enhancement in Heterostructured CdS/ZnO,CdSe/ZnO,and CdTe/ZnO Nanocrystals

A series of highly efficient semiconductor nanocrystal (NC) photocatalysts have been synthesized by growing wurtzite‐ZnO tetrahedrons around pre‐formed CdS, CdSe, and CdTe quantum dots (QDs). The resulting contact between two small but high‐quality crystals creates novel CdX/ZnO heterostructured semiconductor nanocrystals (HSNCs) with extensive type‐II nanojunctions that exhibit more efficient photocatalytic decomposition of aqueous organic molecules under UV irradiation. Catalytic testing and characterization indicate that catalytic activity increases as a result of a combination of both the intrinsic chemistry of the chalcogenide anions and the heterojunction structure. Atomic probe tomography (APT) is employed for the first time to probe the spatial characteristics of the nanojunction between cadmium chalcogenide and ZnO crystalline phases, which reveals various degrees of ion exchange between the two crystals to relax large lattice mismatches. In the most extreme case, total encapsulation of CdTe by ZnO as a result of interfacial alloying is observed, with the expected advantage of facilitating hole transport for enhanced exciton separation during catalysis.     

Studies on Suzuki‐Miyaura Reactions Catalyzed by Ferrocenyl or Cobaltocenyl Phosphines Ligated Palladium Complexes

DFT studies on several dppf ‐ and dppc ‐derived bidentate phosphines ligated palladium complexes catalyzed Suzuki‐Miyaura coupling reactions were pursued. The catalytic reactions employing ligands, having two phosphine biting sites on different cyclpentadienyl or cyclobutadiene rings, such as 1,1′‐dmpf or 1,1′‐dmpc , have been verified to be energetically more favorable than those on the same ring provided that tetra‐coordinated palladium conformations for all transition states and intermediates are maintained. Apart from the purpose of storage, the application of phosphinous acid (R₂P(OH)) in Suzuki‐Miyaura reaction is inferior to tertiary phosphine (R₃P).     

Imidazolin‐2‐ylidenaminophosphines as Highly Electron‐Rich Ligands for Transition‐Metal Catalysts

A variety of chemical transformations benefit from the use of strong electron‐donating ancillary ligands, such as alkylphosphines or N‐heterocyclic carbenes when electron‐rich metal centers are required. Herein, we describe a facile and highly modular access to monodentate and bidentate imidazolin‐2‐ylidenamino‐substituted phosphines. Evaluation of the phosphine’s electronic properties substantiate that the formal replacement of alkyl or aryl groups by imidazolin‐2‐ylidenamino groups dramatically enhance their donor ability beyond that of alkylphosphines and even N‐heterocyclic carbenes. The new phosphines have been coordinated onto palladium(II) centers, and the beneficial effect of the novel substitution patterns has been explored by using the corresponding complexes in the palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction of non‐activated aryl chloride substrates.     

Cation‐Exchanged Resins: Efficient Heterogeneous Catalysts for Facile Synthesis of 1‐Amidoalkyl‐2‐naphthols from One‐Pot,Three‐Component Condensations of Amides/Ureas,Aldehydes, and 2‐Naphthol

One‐pot, three‐component condensation of 2‐naphthol, amides/ureas, and aldehydes takes place smoothly in the presence of cation‐exchange resins to afford the corresponding 1‐amidoalkyl‐2‐naphthols in good yield. Indion‐130 is found to be the best catalyst for the reaction and is recyclable. The method is simple, solvent free, and involves a short reaction time.     

Ylide‐Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis

Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross‐coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron‐rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide‐functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.     

Studies on Suzuki‐Miyaura Reactions Catalyzed by Ferrocenyl or Cobaltocenyl Phosphines Ligated Palladium Complexes

DFT studies on several dppf ‐ and dppc ‐derived bidentate phosphines ligated palladium complexes catalyzed Suzuki‐Miyaura coupling reactions were pursued. The catalytic reactions employing ligands, having two phosphine biting sites on different cyclpentadienyl or cyclobutadiene rings, such as 1,1'‐dmpf or 1,1' ‐dmpc, have been verified to be energetically more favorable than those on the same ring provided that tetra‐coordinated palladium conformations for all transition states and intermediates are maintained. Apart from the purpose of storage, the application of phosphinous acid (R₂P(OH)) in Suzuki‐Miyaura reaction is inferior to tertiary phosphine (R₃P).     

Density functional theory study of calix[4]arene‐N‐azacrown‐5, calix[4]arene‐N‐phenyl‐azacrown‐5, and their complexes with alkali‐metal cations: Na+, K+, and Rb+

Theoretical studies of 1,3‐alternate‐25,27‐bis(1‐methoxyethyl)calix[4]arene‐azacrown‐5 ( L₁ ), 1,3‐alternate‐25,27‐bis(1‐methoxyethyl)calix[4]arene‐N‐phenyl‐azacrown‐5 ( L₂ ), and the corresponding complexes M⁺/ L of L₁ and L₂ with the alkali‐metal cations: Na⁺, K⁺, and Rb⁺ have been performed using density functional theory (DFT) at B3LYP/6‐31G* level. The optimized geometric structures obtained from DFT calculations are used to perform natural bond orbital (NBO) analysis. The two main types of driving force metal–ligand and cation–π interactions are investigated. The results indicate that intermolecular electrostatic interactions are dominant and the electron‐donating oxygen offer lone pair electrons to the contacting RY* (1‐center Rydberg) or LP* (1‐center valence antibond lone pair) orbitals of M⁺ (Na⁺, K⁺, and Rb⁺). What's more, the cation–π interactions between the metal ion and π‐orbitals of the two rotated benzene rings play a minor role. For all the structures, the most pronounced changes in geometric parameters upon interaction are observed in the calix[4]arene molecule. In addition, an extra pendant phenyl group attached to nitrogen can promote metal complexation by 3D encapsulation greatly. In addition, the enthalpies of complexation reaction and hydrated cation exchange reaction had been studied by the calculated thermodynamic data. The calculated results of hydrated cation exchange reaction are in a good agreement with the experimental data for the complexes. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Preparation of weak cation exchange packings based on monodisperse poly(chloromethylstyrene‐co‐divinylbenzene) particles and its chromatographic properties

Monodisperse poly (chloromethylstyrene‐co‐divinylbenzene) particles were firstly prepared by a two‐step swelling method. Based on this media, one kind of weak cation ion exchange packings was prepared. It was demonstrated that the prepared packings have comparative advantages for biopolymer separation with high column efficiency, low interstitial volume and low column backpressure, and have good resolution to proteins. The effects of salt concentration and pH of mobile phase on protein retentions were investigated. The properties of the weak cation ion exchange packings were evaluated by the unified retention model for mixed‐mode interaction mechanism in ion exchange and hydrophobic interaction chromatography.     

Phosphine‐Directed C?H Borylation Reactions: Facile and Selective Access to Ambiphilic Phosphine Boronate Esters

Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium‐catalyzed C H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine‐substituted boronate esters could be deprotected and isolated in pure form.     

Environmentally benign preparation of bifunctional cation exchange fibers

A bifunctional cation exchange fiber was prepared by an efficient and environmentally benign method. In this method, sodium p‐styrene sulfonate (SSS) was cografted directly onto the polypropylene (PP) fiber along with acrylic acid (AA), which eliminated the sulfonation process of grafting fiber with concentrated sulfuric acid or chlorosulfonic acid in the conventional method. Effects of the grafting conditions such as reaction temperature, reaction time, pH value, and the influence of acrylic acid and metallic salt on the graft copolymer reaction were investigated. The physicochemical properties of the cation exchange fibers were characterized with diffuse reflectance infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), X‐ray diffractometer (XRD), thermal gravimetric analysis (TGA), TG‐IR analysis, and monofilament tensile properties test. The experimental results indicate that the optimal conditions of pre‐irradiation grafting are 80°C for 5 hr, and the mechanical properties and thermal stability of the product are better than those of commercial materials (Fiban.K‐1). The total static ion exchange capacity (IEC) of the cationic exchange fiber is up to 5.33 mmol/g. The maximal IEC contribution from the strong acid part is 2.47 mmol/g. This synthetic method provides a clean industrial way for the preparation of bifunctional cation exchange fibers. Copyright © 2009 John Wiley & Sons, Ltd.     

One‐pot synthesis of (3‐sulfopropyl methacrylate potassium)‐silica hybrid monolith via thiol‐ene click chemistry for CEC

A novel (3‐sulfopropyl methacrylate potassium)‐silica hybrid monolithic column for CEC has been prepared by a simple one‐pot approach based on efficient thiol‐ene click chemistry. In this process, the polycondensation of hydrolyzed alkoxysilanes and in situ click reaction of vinyl groups on 3‐sulfopropyl methacrylate potassium and thiol groups on the precondensed siloxanes simultaneously occurred in a pretreated capillary. Homogeneous monolithic matrix with large through‐pores tightly bonded to the inner wall of the capillary was shown by optical microscope and SEM. The minimum plate height of this hybrid monolithic column was determined as 3.9 μm for thiourea. Anilines, alkylbenzenes, and phenols were well separated on this hybrid monolithic column by CEC, which indicated typical reversed‐phase and cation‐exchange chromatographic retention mechanisms of the column.     

Preparation of High‐capacity,Monodisperse Polymeric Weak Cation Exchange Packings Using Surface‐initiated Atom Transfer Radical Polymerization and Its Chromatographic Properties

A novel stationary phase for weak cation exchange (WCX) chromatography was prepared by "grafting from" strategy. Surface initiated atom transfer radical polymerization (ATRP) of acrylic acid (AA) was conducted in toluene medium, starting from the macromolecule initiators of poly(4‐vinylbenzyl chloride‐co‐divinylbenzene) (P_CMS/DVB) beads. The amounts of poly(acrylic acid) grafted chains with different ATRP formulations were calculated based on the elemental analyses. The poly(acrylic acid) grafted beads obtained with different ATRP formulations were tried as chromatographic packings in the separation of proteins by ion‐exchange chromatography. The effect of the poly(acrylic acid) grafted chain lengths on P_CMS/DVB beads for the separation of proteins was investigated in details. Simultaneously, characterization of the column was investigated as ion chromatographic stationary phase for the separation of inorganic cations. The results show that poly(acrylic acid) grafted columns had excellent performance for separation of proteins and inorganic cations. The highest of the dynamic capacity of the column was 35.55 mg/mL. The columns were provided with high column efficiency.     

Organotrifluoroborates and Monocoordinated Palladium Complexes as Catalysts—A Perfect Combination for Suzuki–Miyaura Coupling

Monocoordinated palladium catalysts derived from sterically hindered, electron‐rich phosphines or N‐heterocyclic carbenes have revolutionized the Suzuki–Miyaura coupling reaction. The emergence of organotrifluoroborates has provided important new perspectives for the organoboron component of these reactions. In combination, these two components prove to be extraordinarily powerful partners for cross‐coupling reactions.     

Highly Enantioselective Intramolecular Morita‐Baylis‐Hillman Reaction Catalyzed by Mannose‐Based Thiourea‐phosphine

The saccharide‐based chiral bifunctional thiourea‐phosphines were developed as chiral organocatalysts for the intramolecular Morita‐Baylis‐Hillman reaction of ω‐formyl‐enones. With only 2 mol% of thiourea‐phosphine catalyst 3c , chiral functionalized cyclohexenes were achieved under mild reaction conditions with excellent yields and enantioselectivities.     

5‐phosphorylated 1,2‐disubstituted imidazoles

1,2‐Disubstituted imidazoles react with phosphorus(III) halides in pyridine regioselectively at position 5. The reaction proceeds the more readily, the higher the electron‐donating ability of the 2‐substituent in the starting imidazole. Hitherto unknown dihalo(imidazol‐5‐yl)phosphines have been obtained, and their properties have been studied. Also synthetic methods for the preparation of various monohalo(organyl)(imidazolyl)phosphines have been developed. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:289–308, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20550     

Polymeric herbicide–Montmorillonite composite: synthesis,characterization and release studies

The production of polymeric herbicide intercalated onto montmorillonite interlayer through the process of cation exchange, in order to produce chemically bound polymeric herbicide with clay, has been reported. This was carried out by cation exchange of clay with onium salts of preformed polymeric pentachlorophenyl methacrylate. The products were characterized by various techniques including IR spectroscopy and elemental microanalysis. The interlayer spacing was determined by X‐ray diffraction and thermogravimetric analysis (TGA) and calcination investigated the thermal stability. The morphology of the composite was investigated by scanning electron microscopy. The swelling behaviors in different solvents and release of pentachlorophenol (PCP) in different medium have been described. Copyright © 2001 John Wiley & Sons, Ltd.     

The Usefulness of Trivalent Phosphorus for the Synthesis of Dendrimers

Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents dendrimers constituted of phosphines at each branching point. The other parts display the use of trivalent phosphorus derivatives during the synthesis of dendrimers. Different types of reactions have been applied to phosphines. The very first examples of phosphorus-containing dendrimers were obtained by the alkylation of phosphines. Then, several families of dendrimers were elaborated by reaction of phosphoramidites. Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides. Finally, the Staudinger reaction between phosphines and azides afforded different families of dendrimers, and was at the origin of accelerated methods of synthesis of dendrimers. Besides, the reactivity of the P=N-P=S linkages created by this reaction led to very original dendritic structures.     

Phosphine‐Directed CH Borylation Reactions: Facile and Selective Access to Ambiphilic Phosphine Boronate Esters

Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium‐catalyzed C? H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine‐substituted boronate esters could be deprotected and isolated in pure form.