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Applications of SBA-15 supported Pd metal catalysts as nanoreactors in C-C coupling reactions

Nanoreactors are material structures with engineered internal cavities which create exclusive confined nanoscale surroundings for chemical reactions. The cavities of mesoporous silica SBA-15 can be used as nanoreactors for incorporating catalytic species such as metal nanoparticles, complexes etc. Since SBA-15 silica has a neutral framework, organic functional groups and heteroatoms have been embedded by direct or post-synthesis approaches in order to modify their functionality. Palladium is the most used transition metal for C-C bond formations. Because of the great importance of C-C coupling reactions, this review article aims at providing a deep insight into the state of art in the field of the synthesis and the application of mesoporous SBA-15 silica-supported Pd catalysts in C-C coupling transformations. In most cases, synthesis and modification of the catalyst, time and yield of reactions, recyclability and leaching of the Pd species from the SBA-15 support are discussed to reveal the role of SBA-15 in C-C coupling reactions.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2000

This is a review of papers published in the year 2000 that focus on the synthesis, reactivity, or properties of compounds containing a carbon-transition metal double or triple bond.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Aggregation-induced emission behavior of a pincer platinum(II) complex bearing a poly(ethylene oxide) chain in aqueous solution

An amphiphilic pincer platinum(II) complex with a poly(ethylene oxide) (PEO) chain exhibited aggregation-induced emission (AIE) because of micelle formation in water. The AIE activity was enhanced by the addition of 1,3,5-benzenetricarboxylic acid, which induced micelle formation through hydrogen-bonding interactions with the PEO chain.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Molecular Clusters: Nanoscale Building Blocks for Solid-State Materials

Conspectus The programmed assembly of nanoscale building blocks into multicomponent hierarchical structures is a powerful strategy for the bottom-up construction of functional materials. To develop this concept, our team has explored the use of molecular clusters as superatomic building blocks to fabricate new classes of materials. The library of molecular clusters is rich with exciting properties, including diverse functionalization, redox activity, and magnetic ordering, so the resulting cluster-assembled solids, which we term superatomic crystals (SACs), hold the promise of high tunability, atomic precision, and robust architectures among a diverse range of other material properties. Molecular clusters have only seldom been used as precursors for functional materials. Our team has been at the forefront of new developments in this exciting research area, and this Account focuses on our progress toward designing materials from cluster-based precursors. In particular, this Account discusses (1) the design and synthesis of molecular cluster superatomic building blocks, (2) their self-assembly into SACs, and (3) their resulting collective properties. The set of molecular clusters discussed herein is diverse, with different cluster cores and ligand arrangements to create an impressive array of solids. The cluster cores include octahedral M6E8 and cubane M4E4 (M = metal; E = chalcogen), which are typically passivated by a shell of supporting ligands, a feature upon which we have expanded upon by designing and synthesizing more exotic ligands that can be used to direct solid-state assembly. Building from this library, we have designed whole families of binary SACs where the building blocks are held together through electrostatic, covalent, or van der Waals interactions. Using single-crystal X-ray diffraction (SCXRD) to determine the atomic structure, a remarkable range of compositional variability is accessible. We can also use this technique, in tandem with vibrational spectroscopy, to ascertain features about the constituent superatomic building blocks, such as the charge of the cluster cores, by analysis of bond distances from the SCXRD data. The combination of atomic precision and intercluster interactions in these SACs produces novel collective properties, including tunable electrical transport, crystalline thermal conductivity, and ferromagnetism. In addition, we have developed a synthetic strategy to insert redox-active guests into the superstructure of SACs via single-crystal-to-single-crystal intercalation. This intercalation process allows us to tune the optical and electrical transport properties of the superatomic crystal host. These properties are explored using a host of techniques, including Raman spectroscopy, SQUID magnetometry, electrical transport measurements, electronic absorption spectroscopy, differential scanning calorimetry, and frequency-domain thermoreflectance. Superatomic crystals have proven to be both robust and tunable, representing a new method of materials design and architecture. This Account demonstrates how precisely controlling the structure and properties of nanoscale building blocks is key in developing the next generation of functional materials; several examples are discussed and detailed herein.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Synthesis and Reactivity of Propargylamines in Organic Chemistry

Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C-H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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QUINOLINE DERIVATIVE COMPOUND, METHOD FOR PREPARING SAME, AND PHARMACEUTICAL COMPOSITION CONTAINING SAME

The present invention relates to a novel quinoline derivative compound, an optical isomer thereof, a pharmaceutically acceptable salt thereof, and a hydrate or a solvate thereof. The novel quinoline derivative compound, the optical isomer thereof, the pharmaceutically acceptable salt thereof, and the hydrate or the solvate thereof accelerates gastrointestinal movement, and thus can effectively prevent or treat gastrointestinal mobility disorders.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Molecular engineering of organic reagents and catalysts using soluble polymers

The separation of the final product of a reaction from byproducts, catalysts, or excess reagents is a process common to all synthetic procedures. Various methods to facilitate such separations continue to receive increasing attention as avenues to refine synthetic protocols. This review discusses recent developments in one of these areas, the use of soluble polymers as supports for organic synthesis and catalysis. The general purpose of such work is to combine the principal beneficial features of heterogeneous and homogeneous systems to achieve facile product/catalyst recovery without the polymer affecting the chemistry of known solution-phase processes. The work described here demonstrates that it is often possible to engineer a desired solubility profile, phase behavior, reactivity/selectivity profile, and other beneficial properties into a synthetic reagent or catalyst system by an appropriate choice of soluble polymer support and recovery scheme. In this review, emphasis is given to research published within the last two years.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Selective dimerization of propylene to 2,3-dimethylbutenes by homogeneous catalysts prepared from halogeno(beta-dithioacetylacetonato)nickel(II) complexes containing a highly hindered alkyl phosphine ligand and different aluminium co-catalysts

Halogeno(beta-dithioacetylacetonato)nickel(II) complexes with different alkyl phosphine ligands have been studied in the selective propylene dimerization to 2,3-dimethylbutenes (DMB) in the presence of different organoaluminium compounds. When basic and bulky phosphine ligands, such as tricyclohexyl-(PCy3) and triisopropyl-phosphine (PiPr3) were used in combination with suitable co-catalysts, such as Et3Al2Cl3, Et2AlCl and EtAlCl2/methylalumoxane (MAO), the best results in terms of productivity (up to ~?6,000 h-1) and yield to DMB (up to 68%) were obtained. A detailed analysis of the composition of C9 cut in some selected experiments allowed to evaluate the octane characteristics of the reaction mixture offering both interesting applicative perspectives and mechanistic information.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Geminal Dianions Stabilized by Main Group Elements

This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e., geminal dianions, stabilized by main group elements. Three cases can thus be considered: the geminal-dilithio derivative, for which the two substituents at C are neutral, the yldiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review, the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study

Herein, we report a nickel-1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C-N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald-Hartwig amination process, thus improving the understanding of this important class of reactions.

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Reference£º
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate