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Thermoelectric materials can be used to directly and reversibly convert waste heat into electrical power and have attracted significant attention. Lead-free tin chalcogenide (SnTe, SnSe, SnS) thermoelectric materials are regarded as promising thermoelectric materials due to the great progress in the thermoelectric research field during the past several years. Analogous to PbTe, SnTe has a simple high symmetry NaCl-type cubic structure and a complex band structure, leading to its capability of achieving high thermoelectric performance by band structure and microstructure engineering. SnSe/SnS are simple compounds but exhibit an intrinsically ultralow thermal conductivity, suggesting that a high thermoelectric performance can be realized also in simple layered, anisotropic and anharmonic systems, without nanostructuring. This short perspective summarizes some current strategies that could enhance the thermoelectric performance of bulk lead-free tin chalcogenides, such as band structure engineering, nanostructuring, and synergistically improved approaches. Future possible strategies for further enhancing the thermoelectric performance of tin chalcogenides are also considered at the end of this perspective.

Eight phenylspirodrimane-type analogues, including five new compounds, named stachartins A – E (1, 3, 6 – 8), were isolated from cultures of the tin mine tailings-associated fungus Stachybotrys chartarum. Their structures were elucidated by spectroscopic methods including extensive 2D-NMR techniques.

The title compound (II), a key intermediate for the synthesis of the anti-psychotic drug olanzapine, is prepared by intramolecular cyclocondensation of [(nitrophenyl)amino]thiophenecarbonitrile (I) using tin powder and HCl a reducing system.

Recent progress of η 2 -disilene and η 2 -disilylne mononuclear transition metal complexes and related complexes are summarized. Although examples for disilene-transition metal complexes are still limited for group 4, 6, 8, 10 and 11 metals, η 2 -disilene transition metals complexes have been synthesized by various synthetic methods and structural characteristics are well discussed by using X-ray diffraction analysis, 29 Si NMR resonances and Dewar–Chatt–Duncanson model. Reactions of these complexes have been also investigated. Very recently, η 2 -disilyne-group 10 metal complexes have been synthesized. In addition, transition metal complexes with doubly-bonded silicon compounds such as silenes (R 2 Si CR′ 2 ), silanimines (R 2 Si NR′), silanones (R 2 Si O) and related doubly-bonded germanium and tin compounds as η 2 -ligands are briefly summarized.

Electrochemical energy storage has received a lot of attention due to the common recognition of sustainable development. Nanomaterials are ideal candidates as electrode materials in different fields of energy storage devices, offering favorable transport features, high surface to volume ratio and excellent physicochemical properties. This review is focused on the recent progress in nanostructured Sn-based electrode materials, including Sn, Sn alloys, Sn oxides (SnOx, x = 1, 2), dichalcogenides (SnSx, x = 1, 2) and oxysalts for lithium/sodium-ion batteries and supercapacitors. Sn-based compounds, including SnO, SnO2, MSnxOy (M = Co, Ca, Zn, Mo; x = 1, y = 3), SnS, SnS2, Sn3P4, SnC2O4, SnP2O7, etc., and their composites, possess various valence states and exhibit rich chemistry. They are very attractive candidates for efficient electrochemical energy storage systems because of their unique physicochemical properties, such as conductivity, mechanical and thermal stability, and cyclability. In this review, we aim to provide a systematic summary of the synthesis, modification, and electrochemical performance of nanostructured Sn-based compounds, as well as their energy storage applications in lithium/sodium-ion batteries (LIB/SIB), and supercapacitors. The relationship between nanoarchitectures and electrochemical performances, as well as the related charge-storage mechanism is discussed. Moreover, remarks on the challenges and perspectives of Sn-containing compounds for further development in electrochemical energy storage applications are proposed. This review sheds light on the sustainable development of advanced rechargeable batteries and supercapacitors, with a focus on Sn-based nanomaterials.

Ph3SiSH transforms amides to thioamides and Ph3SnOH performs the reverse process, with the concomitant formation of Ph3SiOH (or Ph3SiOSiPh3) and Ph3SnSSnPh3, respectively. The chemistry is a delightful illustration of the oxophilicity of silicon compared to the thiophilicity of tin and occurs under relatively mild conditions, and for amide to thioamide transformation requires no amide activation. The chemistry is in accord with available data for Si(S)(O), Sn(O)(S) and C(O)(S) bond energies. Copyright © 2016 John Wiley & Sons, Ltd.

The N-alkylation of amines, and amides with benzyl alcohols is catalyzed by bimetallic catalyst [Pd(COD)(SnCl3)Cl] in o-xylene. The reaction does not require additional base, additive or ligand, and is insensitive toward air and moisture and involves minimal work-up. These features make the reaction attractive, simple, and practical.

An efficient process for the synthesis of homoallylic amines and N′-homoallylic hydrazides is developed from the one-pot reaction of carbonyl compounds, amines or N-acylhydrazines, allyllic bromide and tin powder using water as solvent. N-Acylhydrazines are found to be more reactive than amines in these processes. They can react not only with aldehydes but also with ketones to give the corresponding N′-homoallylic hydrazides. Copyright © 2016 John Wiley & Sons, Ltd.

SnAP-eX (tin amine protocol, exocyclic heteroatoms) reagents allow the single-step transformation of aldehydes and ketones into 2,3-disubstituted pyrrolidines and piperidines containing exocyclic amine or alkoxy groups. These saturated N-heterocycles are of importance in modern drug discovery approaches and are prepared in moderate yields using an operationally simple protocol that is compatible with a range of functional groups and heterocyclic aldehydes.

Echoing the recent celebration of the fortieth anniversary of the Barton-McCombie reaction, this review aims to explore another facet of radical processes for deoxygenation of alcohols by considering SET (single electron transfer) reduction of carboxylic ester, thiocarbonate and thiocarbamate derivatives. Various protocols have been developed relying on the use of organic and organometallic SET reagents, electrochemical conditions, photoinduced electron transfer processes and visible-light photoredox catalysis. Applications to the synthesis of molecules of interest provide a glimpse into the scope of these different approaches.

Silicon amine protocol (SLAP) reagents for photocatalytic cross-coupling with aldehydes and ketones to form N-unprotected piperazines have been developed. This blue light promoted process tolerates a wide range of heteroaromatic, aromatic, and aliphatic aldehydes and structurally and stereochemically complex SLAP reagents. It provides a tin-free alternative to SnAP (tin amine protocol) reagents for the synthesis of substituted piperazines.

Tin phosphides make up a class of materials that have received a noteworthy amount of interest in photocatalysis, charge storage, and thermoelectric devices. Dual stable oxidation states of tin (Sn2+ and Sn4+) allow tin phosphides to exhibit different stoichiometries and crystal phases. However, the synthesis of such nanostructures with control over morphology and crystal structure has proven to be a challenging task. Herein, we report the first colloidal synthesis of size-, shape-, and phase-controlled, narrowly disperse rhombohedral Sn4P3, hexagonal SnP, and trigonal Sn3P4 nanoparticles (NPs) displaying tunable morphologies and size-dependent physical properties. The control over NP morphology and crystal phase was achieved by tuning the nucleation/growth temperature, Sn/P molar ratio, and incorporation of additional coordinating solvents (alkylphosphines). The absorption spectra of Sn3P4 NPs (3.0 ± 0.4 to 8.6 ± 1.8 nm) exhibit size-dependent blue shifts in energy gaps (1.38–0.88 eV) compared to the the...

A facile entry to α-chloro-β-hydroxy ketone derivatives via SnCl 4 ·5H 2 O-catalyzed regioselective chlorohydroxylation of α,β-unsaturated carbonyl compounds is described. This reaction proceeded in water and is a rare example of Selectfluor serving as a chlorine source. The utility of the products was highlighted by the transformations to β-dicarbonyl compound and highly substituted 1,4-dioxane derivative. Some mechanistic investigations were also carried out, which suggested that a radical pathway was more likely to be involved.

A unique preference of tin(II) for aniline activation is disclosed. In the present work tin(II) triflate-catalyzed highly selective Markovnikov reductive hydroamination of internal as well as terminal alkynes is reported. The mechanistic study revealed the involvement of two steps in one pot wherein alkyne reduces to corresponding alkene in presence of PMHS as reducing agent followed by hydroamination of alkene. A broad range of alkynes transformed into tertiary amines with good to excellent yield. This method is equally applicable in synthesis of secondary amines.

Mono-arsenide CrAs, endures a helical anti-ferromagnetic order transition at ∼265 K under ambient pressure. Recently, pressure-induced-superconductivity was discovered vicinity to the helical anti-ferromagnetic order in CrAs [Wei Wu et al., Nature Communications 5, 5508 (2014).]. However, the size of crystal grown via tin flux method is as small as 1 mm in longest dimension. In this work, we report the single crystal growth of CrAs with size of 1 × 5 × 1 mm3 via chemical vapor transport method and its physical properties.

Tin(IV) bromide was found to act as an efficient Lewis acid catalyst for the Friedel–Crafts type dehydrative alkylation reaction of diarylmethanols with 2-naphthol derivatives under mild conditions. The effects of the substituents on the substrates were systematically evaluated, and the reaction could be applied to a variety of substrates by tuning the conditions depending on the electronic properties of the starting materials.

Starting from Sn(I) halides, available via a preparative co-condensation technique, we have established a fruitful route to metalloid tin clusters in recent years. Applying a Sn(I)Cl solution, we w...

An efficient multicomponent one-pot reaction was developed for the synthesis of α,α-disubstituted homoallylic hydrazides by treating ketones, acylhydrazines and allyl bromide with tin powder in tetrahydrofuran under reflux. The reaction proceeds smoothly without any catalyst under mild conditions to give the corresponding products in high yields.

A tin-catalyzed reaction of α-hydroxy ketones with 1,1-dicyanoalkenes produced 2-amino-4,5-dihydrofuran-3-nitriles. In the catalytic reaction, tin enolates were generated from α-hydroxy ketones as active catalytic species. The highly basic ability of the Sn-O bonds played an important role in the reactions. This tin-catalyzed reaction was highly atom-economical and required no other metal reagents.

An efficient and convenient one-pot method for the preparation of trifluoromethylated homoallylic N-acylhydrazines or α-methylene-γ-lactams has been described. In this process, allyl bromide and metal tin are used instead of toxic stannanes, and commercially available aqueous trifluoroacetaldehyde methyl hemiacetal was used as a trifluoromethyl source.

TiN2 is prepared in a laser-heated diamond anvil cell using pre-compressed TiN flakes surrounded by a dense N2 pressure transmitting medium (Re gaskets, 73 GPa, 2400 K).

Lead-free CsSnX3 (X: Br, Cl, I) and mixed halide perovskites of different compositions are obtained as thin films by coating e.g. glass substrates with stoichiometric solutions of CsX and SnX2 in DMF (70 °C, 12 h).

A concise and efficient method for the synthesis of α-methylene-γ-lactams is developed from multicomponent one-pot reactions of aldehydes or ketones, hydrazides, and ethyl 2-(bromomethyl)acrylate promoted by tin powder. The reaction proceeds smoothly under mild reaction conditions without using any catalyst to give the corresponding products in high yields. α-Methylene-γ-spirolactams can also be prepared from cyclic ketones.

The synthesis of crystals of a zinc- and tin-based earth-abundant element nitride (ZnSnN2) semiconductor was successfully achieved via a metathesis reaction under high pressure. Pressures exceeding 5.5 GPa were required to obtain single-phase crystals. The material's bandgap was determined to be 1.4 eV, which is ideal for photovoltaic absorbers and visible light-active photocatalysts. The decomposition temperature of the material was estimated to be approximately 350‒400 °C at atmospheric pressure. Finally, the chemical stability of the material against alkali and acid solutions was sufficient for photovoltaic and photocatalytic applications.

A copper complex has proven to be a potent catalyst for forming a C-B bond via diborylation of arynes and alkynes, affording vic-diborylarenes and vic-diborylalkenes with high efficiency. A boryl-substituted organocopper species, which is intermediately generated in the diborylation, has been found to be captured by a tin or a carbon electrophile, leading to three-component borylstannylation or carboboration, in which C-B and C-Sn (or C) bonds are constructed simultaneously. Furthermore, reducing the Lewis acidity of the boron center with 1,8-diaminonaphthalene decisively alters the regiochemical behavior of the borylcopper species, enabling the installation of a boryl moiety to occur at an internal carbon of terminal alkynes in borylstannylation and protoboration. Copper catalysis for C-Sn and C-Si bond-forming processes via distannylation, hydrostannylation and silylstannylation, as well as silver catalysis for a C-B bond-forming reaction, is also described.

Simple and abundant carboxylic acids have been used as acyl radical precursor by means of visible-light photoredox catalysis. By the transient generation of a reactive anhydride intermediate, this redox-neutral approach offers a mild and rapid entry to high-value heterocyclic compounds without the need of UV irradiation, high temperature, high CO pressure, tin reagents, or peroxides.

We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.

Data on the phase diagram, preparation procedures, thermodynamic properties, and electrochemical characteristics of liquid and solid lithium-tin alloys are summarized and analyzed. The use of lithium-tin alloys in various chemical current sources is considered. The prospects for using tin, its alloys, and compounds as anode material in lithium-ion batteries are briefly discussed.

Transmetalation of Me3Sn-substituted azobenzenes with MeLi results in a rapid and selective Li-Sn exchange.

The transition metal-catalyzed cross-coupling of organometallic nucleophiles derived from tin, boron, and zinc with organic electrophiles enjoys a preeminent status among modern synthetic methods for the formation of carbon–carbon bonds. In recent years, organosilanes have emerged as viable alternatives to conventional reagents, with the added benefits of low cost, low toxicity, and high chemical stability. However, silicon-based cross-coupling reactions often require heating in the presence of a fluoride source, which has significantly hampered their widespread acceptance. To address the “fluoride problem”, a new paradigm for palladium-catalyzed, silicon-based cross-coupling reactions has been developed that employs a heretofore underutilized class of silicon reagents, the organosilanols. The use of organosilanols, either in the presence of Bronsted bases or as their silanolate salts, represents an operationally simple and mild alternative to the fluoride-based activation method. Organosilanols are readi...

TiN porous layers and Fe2N nanoparticles are grown on vertically aligned graphene nanosheets by atomic layer deposition and used as the cathode and anode for asymmetric solid-state supercapacitors, respectively.

A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).

The cyclocondensations are performed in molten tin dichloride which acts as both reaction medium and Lewis acid catalyst.

Reversed regioselectivity, compared to conventional silylstannylation reactions under Pd-catalysis, is achieved using silyl boranes (II) and tin alkoxides (III) and (VII) in a one-pot reaction to generate either 2-silyl-1-stannyl-1-alkenes (IV)/(V) from alkynes (I) and 1-silyl-2-stannyl-2-alkenes (VIII)/(IX) from allenes (VI).

Hydrostannation of vinylcyclopropanes (VCPs) followed by reaction with aldehydes gives access to homoallylic alcohols without the use of transition-metal catalysts.

A tin-free trans-Diels–Alder paradigm for the stereoselective synthesis of trans-fused polycyclic systems was developed through the photocatalytic reductive dehalogenation of α-haloketones promoted by visible light. Good to excellent diastereoselectivities were observed in the stereoselective construction of trans-fused octalone derivatives under mild reaction conditions.

Heterobimetallic catalysts, bearing a metal–metal bond between a transition metal (TM) and a tin atom, are very promising due to their ability in mediating a wide variety of organic transformations. Indeed the utilization of such catalysts is a challenging and evolving area in the field of homogeneous catalysis. Catalysis across a ‘TM–Sn’ motif is an emerging area in the broader domain of multimetallic catalysis. The present review apprises the chemists' community of the past, present and future scope of this versatile catalytic motif. The TM–Sn catalyzed reactions presented include, among others, Friedel–Crafts alkylation, carbonylation, polymerization, cyclization, olefin metathesis, Heck coupling, hydroarylation Michael addition and tandem coupling. The mechanistic aspects of the reactions have been highlighted as well.

Homoallylic alcohols (III), (V) are obtained by allylation of the various substituted aldehydes or ketones using high purity Sn(0) as catalyst.

Single crystals of (IIIa—e) and (V) are hydrothermally grown and characterized by single crystal XRD, IR and UV/VIS spectroscopy, SEM, second harmonic generation measurements, and piezoelectric and polarization measurements.

The mild protocol does not require toxic or hazardous reagents and tolerates a variety of functional groups including acid and base labile ones.

[Sn(H2O)3](ClO4)2 is prepared by the redox reaction of Cu(ClO4)2 and Sn in HClO4 followed by crystallization in a freezer (253 K).

Newly developed catalysts are shown to be superior to known catalysts in the cyclotrimerization of arylisocyanates.

In reactions of allylgermanes with aldehydes promoted by tin(IV) halides 1,5- and 1,6- stereocontrol is achieved.

The photocatalyzed redox deoxygenation of o-thiocarbamates of secondary, tertiary, and benzylic alcohols with good functional group tolerance is developed.

Thermal radical reactions (reduction, Giese reaction) are studied on halosugars and α-bromoamides.

trans-2-Aryl-3-nitro-cyclopropane-1,1-dicarboxylates when reacted with nitriles in the presence of tin(IV) chloride afford 2,4,5-trisubstituted oxazoles in good to excellent yields. The reactions take place through in situ generation of aroylmethylidene malonates from the cyclopropanes, followed by conjugate addition of nitriles to the malonates to form nitrilium ion intermediates and subsequent cyclisation.