Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Base-induced reversible H₂ addition to a single Sn(ii) centre.

ABSTRACT: A range of amines catalyse the oxidative addition (OA) of H₂ to [(Me₃Si)₂CH]₂Sn (1), forming [(Me₃Si)₂CH]₂SnH₂ (2). Experimental and computational studies point to 'frustrated Lewis pair' mechanisms in which 1 acts as a Lewis acid and involve unusual late transition states; this is supported by the observation of a kinetic isotope effect for Et₃N. When DBU is used the energetics of H₂ activation are altered, allowing an equilibrium between 1, 2 and adduct [1·DBU] to be established, thus demonstrating reversible oxidative addition/reductive elimination (RE) of H₂ at a single main group centre.

SUBMITTER: Turnell-Ritson RC

PROVIDER: S-EPMC6289099 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Base-induced reversible H2 addition to a single Sn(ii) centre.

Turnell-Ritson Roland C RC Sapsford Joshua S JS Cooper Robert T RT Lee Stella S SS Földes Tamás T Hunt Patricia A PA Pápai Imre I Ashley Andrew E AE

Chemical science 20180918 46

A range of amines catalyse the oxidative addition (OA) of H2 to [(Me3Si)2CH]2Sn (1), forming [(Me3Si)2CH]2SnH2 (2). Experimental and computational studies point to 'frustrated Lewis pair' mechanisms in which 1 acts as a Lewis acid and involve unusual late transition states; this is supported by the observation of a kinetic isotope effect for Et3N. When DBU is used the energetic ...[more]

PMID: 30627391

Similar Datasets

Current-Induced Reversible Split of Elliptically Distorted Skyrmions in Geometrically Confined Fe3 Sn2 Nanotrack.

Project description:Skyrmions are swirling spin textures with topological characters promising for future spintronic applications. Skyrmionic devices typically rely on the electrical manipulation of skyrmions with a circular shape. However, manipulating elliptically distorted skyrmions can lead to numerous exotic magneto-electrical functions distinct from those of conventional circular skyrmions, significantly broadening the capability to design innovative spintronic devices. Despite the promising potential, its experimental realization so far remains elusive. In this study, the current-driven dynamics of the elliptically distorted skyrmions in geometrically confined magnet Fe3 Sn2 is experimentally explored. This study finds that the elliptical skyrmions can reversibly split into smaller-sized circular skyrmions at a current density of 3.8 × 1010 A m-2 with the current injected along their minor axis. Combined experiments with micromagnetic simulations reveal that this dynamic behavior originates from a delicate interplay of the spin-transfer torque, geometrical confinement, and pinning effect, and strongly depends on the ratio of the major axis to the minor axis of the elliptical skyrmions. The results indicate that the morphology is a new degree of freedom for manipulating the current-driven dynamics of skyrmions, providing a compelling route for the future development of spintronic devices.

| S-EPMC10037979 | biostudies-literature

Light-induced reversible reorganizations in closed Type II reaction centre complexes: physiological roles and physical mechanisms.

Project description:The purpose of this review is to outline our understanding of the nature, mechanism and physiological significance of light-induced reversible reorganizations in closed Type II reaction centre (RC) complexes. In the so-called 'closed' state, purple bacterial RC (bRC) and photosystem II (PSII) RC complexes are incapable of generating additional stable charge separation. Yet, upon continued excitation they display well-discernible changes in their photophysical and photochemical parameters. Substantial stabilization of their charge-separated states has been thoroughly documented-uncovering light-induced reorganizations in closed RCs and revealing their physiological importance in gradually optimizing the operation of the photosynthetic machinery during the dark-to-light transition. A range of subtle light-induced conformational changes has indeed been detected experimentally in different laboratories using different bRC and PSII-containing preparations. In general, the presently available data strongly suggest similar structural dynamics of closed bRC and PSII RC complexes, and similar physical mechanisms, in which dielectric relaxation processes and structural memory effects of proteins are proposed to play important roles.

| S-EPMC9748786 | biostudies-literature

Crystal Structures of a Cubic Tin(II) Germanate, α-Sn6GeO8, and a Tetragonal Tin(II) Silicate, γ-Sn6SiO8.

Project description:A cubic tin(II) germanate, α-Sn6GeO8 (space group F4̅3m, a = 10.52521(2) Å, and Z = 4), has been synthesized by both regular hydrothermal and microwave-assisted hydrothermal methods, and the crystal structure of this material has been solved by Rietveld refinement of synchrotron powder X-ray diffraction (PXRD) data. The crystal structure is analogous to α-Sn6SiO8 and is therefore related to the zinc blende structure comprising a face-centered cubic array of [Sn6O8]4- anionic clusters with Ge4+ cations occupying half of the tetrahedral holes. Variable-temperature PXRD has revealed that tin(II) germanate has high thermal stability: remaining stable at 950 K and mostly decomposing over the range 984-1034 K. The tin(II) germanate has been further characterized by X-ray fluorescence (XRF), Raman, and diffuse reflectance (DR) UV-vis spectroscopies. In addition, variable-temperature PXRD studies have revealed the formation of a tetragonal tin(II) silicate polymorph, γ-Sn6SiO8 (space group I4̅, a = 7.30414(6) Å, c = 10.53731(6) Å, and Z = 2), at temperatures below 170 K. The crystal structure of γ-Sn6SiO8 has been elucidated by Rietveld refinement. While a transition to a tetragonal polymorph is observed upon cooling α-Sn6SiO8, no corresponding transition is observed for α-Sn6GeO8, which retains its cubic structure over the probed temperature range.

| S-EPMC9490749 | biostudies-literature

Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn(ii)/Sn(iv) doping.

Project description:Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(iii) ions by equal quantities of Sn(ii) and Sn(iv). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(ii) and Sn(iv) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(ii) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(ii) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure-property relationships of lead-free vacancy-ordered perovskite structures.

| S-EPMC8597838 | biostudies-literature

Isolation of an Anionic Dicarbene Embedded Sn2 P2 Cluster and Reversible CO2 Uptake.

Project description:Decarbonylation of a cyclic bis-phosphaethynolatostannylene [(ADC)Sn(PCO)]2 based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C}2 ; Dipp = 2,6-iPr2 C6 H3 ) under UV light results in the formation of a Sn2 P2 cluster compound [(ADC)SnP]2 as a green crystalline solid. The electronic structure of [(ADC)SnP]2 is analyzed by quantum-chemical calculations. At room temperature, [(ADC)SnP]2 reversibly binds with CO2 and forms [(ADC)2 {SnOC(O)P}SnP]. [(ADC)SnP]2 enables catalytic hydroboration of CO2 and reacts with elemental selenium and Fe2 (CO)9 to afford [(ADC)2 {Sn(Se)P2 }SnSe] and [(ADC)Sn{Fe(CO)4 }P]2 , respectively. All compounds are characterized by multinuclear NMR spectroscopy and their solid-state molecular structures are determined by single-crystal X-ray diffraction.

| S-EPMC10837339 | biostudies-literature

Dynamic reversible adhesives based on crosslinking network via Schiff base and Michael addition.

Project description:It is of practical interest to obtain polymers with complex material properties in a simplified synthetic manner for a broader range of practical applications. In this work, we constructed a dynamic reversible adhesive based on branched polyamine (PA) and p-formylphenyl acrylate (FPA) by simultaneously performing Michael addition reaction and Schiff base reaction. Branched polyamines provide a large number of amino groups as reaction sites that can react with both carbon-carbon double bonds and aldehyde groups. This enables the branched polymeric adhesive system to have a large number of Schiff base bonds within it, an important property of Schiff base bonds is that they are dynamically reversible. This allows us to prepare adhesives with hyperbranched crosslinking networks and recycling properties, and we have verified that FPA-PA adhesives do not exhibit significant fatigue after multiple recycling through the gluing-destruction-gluing process. The resulting FPA-PA adhesives produce tough bonding on multi-substrates such as steel, aluminum, glass, PVC, PTFE, birch and moso bamboo, which exhibited by lap shear strength of 2.4 MPa, 1.7 MPa, 1.4 MPa, 1.3 MPa, 0.4 MPa, 1.6 MPa, and 1.8 MPa, respectively. The feasibility of the synthesis idea of simultaneous Michael addition reaction and Schiff base reaction was demonstrated, as well as the excellent performance and great application potential of FPA-PA adhesives to be recyclable on multi-substrates.

| S-EPMC9116177 | biostudies-literature

Photochemical formation and reversible base-induced cleavage of a phosphagallene.

Project description:The reactivity of Cp*Ga (Cp* = C5Me5) towards phosphanylidenephosphoranes of the type ArTerP(PMe3) (ArTer = DipTer 2,6-(2,6-iPr2C6H3)2C6H3), TipTer 2,6-(2,4,6-iPr3C6H2)2C6H3 was investigated. While no thermal reaction was observed (in line with DFT results), irradiation at 405 nm at low temperatures resulted in the formation of phosphagallenes DipTerP = GaCp* (1a) and TipTerP = GaCp* (1b) accompanied by release of PMe3. When warming the reaction mixture to ambient temperatures without irradiation, the clean re-formation of ArTerP(PMe3) and Cp*Ga in a second-order reaction was observed. Upon removal of PMe3, 1a and 1b were isolated and fully characterized. Both derivatives were found to be labile and decomposed to the phosphafluorenes 2a and 2b, indicating generation of the transient phosphinidene ArTerP along with Cp*Ga. First reactivity studies show that CO2 and H2O cleanly reacted with 1a, affording DipTerPCO (3) and DipTerPH2 (4), respectively.

| S-EPMC10016425 | biostudies-literature

Reversible Diels-Alder Addition to Fullerenes: A Study of Dimethylanthracene with H2@C60.

Project description:The study of isolated atoms or molecules inside a fullerene cavity provides a unique environment. It is likely to control the outer carbon cage and study the isolated species when molecules or atoms are trapped inside a fullerene. We report the Diels-Alder addition reaction of 9,10-dimethyl anthracene (DMA) to H2@C60 while 1H NMR spectroscopy is utilized to characterize the Diels-Alder reaction of the DMA with the fullerene. Through 1H NMR spectroscopy, a series of isomeric adducts are identified. The obtained peaks are sharp, precise, and straightforward. Moreover, in this paper, H2@C60 and its isomers are described for the first time.

| S-EPMC9144212 | biostudies-literature

Reversible Oxidative Addition of Zinc Hydride at a Gallium(I)-Centre: Labile Mono- and Bis(hydridogallyl)zinc Complexes.

Project description:In the presence of TMEDA (N,N,N',N'-tetramethylethylenediamine), partially deaggregated zinc dihydride as hydrocarbon suspensions react with the gallium(I) compound [(BDI)Ga] (I, BDI={HC(C(CH3 )N(2,6-iPr2 -C6 H3 ))2 }- ) by formal oxidative addition of a Zn-H bond to the gallium(I) centre. Dissociation of the labile TMEDA ligand in the resulting complex [(BDI)Ga(H)-(H)Zn(tmeda)] (1) facilitates insertion of a second equiv. of I into the remaining Zn-H to form a thermally sensitive trinuclear species [{(BDI)Ga(H)}2 Zn] (2). Compound 1 exchanges with polymeric zinc dideuteride [ZnD2 ]n in the presence of TMEDA, and with compounds I and 2 via sequential and reversible ligand dissociation and gallium(I) insertion. Spectroscopic and computational studies demonstrate the reversibility of oxidative addition of each Zn-H bond to the gallium(I) centres.

| S-EPMC9804236 | biostudies-literature

Mechanically induced cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers.

Project description:Mechanoredox catalysis has emerged as a sustainable approach for organic transformations. Mechanically controlled polymerization that uses mechanoredox catalysts enables synthesis of complex polymers and mechanoresponsive materials with diverse applications. Despite its potential, the focus has predominantly been on free radical polymerization and acrylate monomers. The mechanochemical synthesis of poly(vinyl ether)s (PVEs) poses a significant challenge in the field. Herein, we report an efficient mechanically induced cationic reversible addition-fragmentation chain transfer (mechano-cRAFT) polymerization using 2D MoS2 as a mechanoredox catalyst, where free radical intermediates can be further oxidized to cations to promote cationic polymerization of vinyl ethers. This mechano-cRAFT polymerization can be conducted in air and with minimal organic solvent, resulting in quantitative monomer conversion. This strategy is applicable to a range of vinyl ether monomers, yielding polymers with controlled molecular weight and narrow dispersity. We also performed trapping experiments to investigate the piezoelectrically mediated redox process, and further validated the mechanism through density functional theory (DFT) calculations.

| S-EPMC11514177 | biostudies-literature