Durable Superhydrophobic Surfaces with Self-Generated Wenzel Sites for Efficient Fog Collection.

Harvesting freshwater from fog is one of the possible solutions to the global water scarcity crisis. Surfaces with both hydrophobic and hydrophilic regions are extensively employed for this purpose. Nevertheless, the longevity of these surfaces is still constrained by their delicate surface structures. The hydrophilic zones may become damaged or contaminated after repeated use, thereby compromising their effectiveness in fog collection. The preparation of generally applicable durable superhydrophobic coatings with self-generated Wenzel sites is reported here for long-term efficient and stable fog collection. The coatings are prepared by depositing the poly(tannic acid) coating as the primer layer on various substrates, self-assembly of trichlorovinylsilane into staggered silicone nanofilaments, and then thiol-ene click reaction with 1H,1H,2H,2H-perfluorodecanethiol. The coatings demonstrate remarkable static superhydrophobicity, robust impalement resistance, and stable self-generated Wenzel sites for water droplets. Therefore, the fog collection rate (FCR) of the coatings reaches 2.13 g cm-2 h-1 during 192 h continuous fog collection, which is triple that of bare substrate and outperforms most previous studies. Moreover, the systematic experiments and models have revealed that the key factors for achieving high FCR on superhydrophobic coatings are forming condensed droplets ≈1 mm in critical radius and a Wenzel site proportion of 0.3-0.4.

Poly(vinyl chloride) Dechlorination Catalyzed by Zirconium.

Poly(vinyl chloride) undergoes dechlorination in the presence of triethylsilane (Et3SiH) and a catalytic amount of [Cp2Zr(NPh2)][CH3B(C6F5)3] (1 b) at 40-80 °C, with up to 91 % efficiency. Stoichiometric reactivity studies conducted on cyclohexyl chloride as a model suggest that 1 b dechlorinates PVC by initial chloride abstraction, followed by hydride transfer to the cationic PVC chain from Et3SiH. Consumer items such as pipe fitting, vinyl disc or electric cable insulation undergo either dechlorination or hydrosilylation of the carbonyl-containing copolymer (polyvinyl acetate) or plasticizer (phthalate).

Challenges in the Synthesis and Processing of Hydrosilanes as Precursors for Silicon Deposition.

Hydrosilanes are highly attractive compounds, which can be processed as liquids with printing technology to amorphous silicon films on nearly any solid substrate. The silicon layers can be processed for electronic devices like transistors or thin-film solar cells. The endothermic character of hydrosilanes with their positive enthalpies of formation results in favorable properties for processing. The larger the molecules, the lower their decomposition temperature and the higher their photoactivity. Cyclic hydrosilanes such as cyclopentasilane and cyclohexasilane can be easily deposited. The branched neopentasilane is more difficult to deposit but yields better-quality films after processing. The key challenge is the complex synthesis of the precursors and the hydrosilanes. The available preparative methods are presented in this review and their advantages and disadvantages are evaluated. The following synthesis methods are presented and discussed in this article: Wurtz coupling and other reductive coupling processes, dehydrogenative coupling of silanes, plasma synthesis of chlorinated polysilanes, amine- or chloride-induced disproportionations, and transformation of monosilane to higher silanes. Plasma synthesis is already carried out today as a continuous industrial process. The most effective synthesis methods in the laboratory are currently amine- and chloride-induced disproportionations. There is a great need to further optimize the syntheses of hydrosilanes and to develop new simple synthesis variants.

A Heteroatom-Containing Functional Poly(Silylenevinylene): Synthesis, Anion Binding, and Sensing of Anion Extraction Processes.

Catalytic hydrosilylation is one of the important synthetic approaches to prepare functional organosilicon polymers. Herein, a functional silicon copolymer is constructed by polyhydrosilylation reaction between a novel 3,7-bis(dimethyl silane)-10-(2-ethylhexyl)-10H-phenothiazine monomer and a neutral tetrapyrrolic macrocycle, namely, 5,5,10,15,15,20-hexamethyl-10α, 20α-bis(4-[ethynylphenyl]) calix[4]pyrrole. The as-constructed copolymer (Mn  = 9609, PDI = 2.2) is investigated as an extractant for organic anions as their tetrabutylammonium salts under interfacial aqueous-organic (water-chloroform) conditions. In this context, a distinctive naked-eye colorimetric as well as fluorescence detection method is developed based on anion-directed hydrogen-bonding interactions. This kind of color/fluorescence monitoring serves as a handy tool for rapid screening of anion extraction processes. The copolymer exhibits high selectivity toward extraction of chloride anion. This study augments the field of polycarbosilanes, poly(silylenevinylene)s in particular, allowing access to a new application window that can be further advanced with good grace in near future.

Catalyst-Free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide.

Radical trifluoromethoxylation is an attractive approach to prepare compounds featuring the important OCF3 group, however most existing methods have focused on aromatic substrates. Here, we report novel methodologies with alkenyl substrates employing bis(trifluoromethyl)peroxide (BTMP) as a practical and comparatively atom economical trifluoromethoxylating reagent. With silyl enol ether substrates, switching reaction solvent allows for the synthesis of either α-(trifluoromethoxy)ketone products or unprecedented alkenyl-OCF3 species. Furthermore, allyl silanes have been employed as substrates for the first time, affording allyl(trifluoromethyl)ether products in good yields. In each case, the methods operate at room temperature without large excesses of the alkene substrate while, in contrast to previous radical trifluoromethoxylation reactions, no catalyst, light or other activators are required.

B(C6 F5 )3 -Catalyzed Regioselective Ring Opening of Cyclic Amines with Hydrosilanes.

Opening the ring of cyclic amines by regioselective fission of one of the carbon-nitrogen bonds greatly expands the repertoire of available nitrogen-containing skeletons. Unlike approaches starting from cyclic tertiary amines, methods that can directly open secondary amines are still scarce. The present work discloses an efficient reductive ring opening of either of these cyclic amines using PhSiH3 under B(C6 F5 )3 catalysis. By this, the direct transformation of unstrained cyclic amines into the corresponding acyclic amines is achieved in a simple one-pot operation. A stepwise mechanism proceeding through the intermediacy of silylammonium ions followed by reductive cleavage of a carbon-nitrogen bond was experimentally verified.

Base-Mediated Radio-Iodination of Arenes by Using Organosilane and Organogermane as Radiolabelling Precursors.

The radio-iodination of arenes is investigated from organosilane and organogermane precursors using ipso-electrophilic halogenation (IEH). Discovery of a mild base mediated process allows radio-iodination in HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) of either aryl silane or germane, with germanes being more reactive. Clinical potential of arylgermanes as radio-iodination precursors is demonstrated through the labelling of [125 I]IMTO (iodometomidate) and [125 I]MIBG (meta-iodobenzylguanidine) thus offering an alternative to radio-iododestannylation processes using non-toxic precursors.

Group I Alkoxides and Amylates as Highly Efficient Silicon-Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes.

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KOt Amyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3 SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition-metal catalysts for this transformation. Preliminary evidence suggests the formation of hypercoordinated intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si-N bond formation.

Small Molecule Activation on a Base-stabilized Phosphinidene.

Reduction of (NP)PCl2 (NP=phosphinoamidinate [PhC(NAr)(=NPPri 2 )]- ) with KC8 affords the phosphinoamidinato-supported phosphinidene (NP)P (9). Reaction of 9 with a N-heterocyclic carbene (MeC(NMe))2 C: results in the NHC-adduct NHC→P-P(Pri 2 )=NC(Ph)=NAr featuring an iminophosphinyl group. Reactions of 9 with HBpin and H3 SiPh led to the metathesis products (NP)Bpin and (NP)SiH2 Ph, respectively, whereas with HPPh2 a base-stabilized phosphido-phosphinidene, the product of N-P and H-P bond metathesis, was obtained. Reaction of 9 with tetrachlorobenzaquinone results in oxidation of P(I) to P(III), accompanied by oxidation of the amidophosphine ligand into P(V). Addition of benzaldehyde to 9 results in a phospha-Wittig reaction affording a product of P=P and C=O bond metathesis. Related reaction with phenylisocyanate results in a product of N-P(=O)Pri 2 addition to the C=N bond of an intermediate iminophosphaalkene to produce a phosphinidene intramolecularly stabilized by a diaminocarbene.

Assessing Combinations of B(C6 F5 )3 and N2 -Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation.

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage their N ligand in dative bonding with the strong Lewis acid B(C6 F5 )3 . The stable adducts were assessed for frustrated Lewis pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6 F5 )2 . Whereas Si-H bond activation was achieved, HB(C6 F5 )2 was shown to substitute B(C6 F5 )3 in a quantitative or equilibrated fashion, depending on the nature of the nitrido complex. No B-H bond splitting was observed. Thermodynamics of these reactions, computed by DFT, are in agreement with the experimental outcomes.

Chiral Silanols: Strategies and Tactics for Their Synthesis.

Silanols are valuable and important compounds, which have found widespread applications in the field of materials science, synthetic chemistry, and medicinal chemistry. Although a handful of approaches have been developed for the synthesis of various silanols, access to enantioenriched silicon-stereogenic silanols remains underdeveloped. This Concept article intends to summarize and highlight recent advances in the construction of silicon-stereogenic silanols and endeavors to encourage further research in this area.

Reversible Transition between Discrete and 1D Infinite Architectures: A Temperature-Responsive Cu(I) Complex with a Flexible Disilane-Bridged Bis(pyridine) Ligand.

A thermoresponsive structural change based on a disilane-bridged bis(pyridine) ligand and CuI is reported. Single-crystal X-ray analysis revealed that there are two polymorphs in the Cu(I) complex: octanuclear copper(I) complex at 20 °C and 1D staircase copper(I) polymer complex at -173 °C. The formation of these polymorphs is due to the flexibility of the ligand. Cu-I bond formation is observed upon cooling the sample from -10 °C to -170 °C. The temperature-induced phase transition progression was clarified by DSC, VT-PXRD, and VT-photoluminescence measurements and indicated a reversible temperature-controlled crystal-to-crystal phase transition. Observation on a VT-stage using a high-speed camera showed crystal cracking during single-crystal to single-crystal transitions between these polymorphic forms.

Recent Progress in the Synthesis of Silaspiranes.

Silaspiranes bearing a spiro-silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development of efficient methods towards these ring structures has therefore attracted considerable attentions of synthetic chemists. This minireview highlights the representative advances in the field, and is categorized into four parts according to the ring formation strategies: cyclization, annulation, ring expansion and cycloaddition.

Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study.

In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties. To achieve that, several tetrafluorophenyl silane derivatives have been substituted at the meta and para positions by several electron donating and electron withdrawing groups (EDG and EWG, respectively), such as -NH2, -OCH3, -CH3, -H, -CF3 and -CN substituents. As electron donor molecules, we have used a series of hydrogen cyanide derivatives using the same EDGs and EWGs. We have obtained the Hammett's plots for different combinations of donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammet's σ parameter). In addition, we have used the electrostatic potential (ESP) surface analysis as well as the Bader's theory of atoms in molecules (AIM) and noncovalent interaction plot (NCI plot) techniques to further characterize the TtBs studied herein. Finally, a Cambridge Structural Database (CSD) inspection was carried out, retrieving several structures where halogenated aromatic silanes participate in tetrel bonding interactions, being an additional stabilization force of their supramolecular architectures.

Iron-Catalyzed Reductive Cross-Coupling of Alkyl Electrophiles with Olefins.

In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl-alkyl bond construction is central to organic synthesis, examples of iron-catalyzed alkyl-alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross-coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents. Carbon-carbon bond formation proceeds at room temperature, and the method employs commercially available components (Fe(OAc)2 , Xantphos, and Mg(OEt)2 ); interestingly, this set of reagents can be applied directly to a distinct hydrofunctionalization of olefins, hydroboration. Mechanistic studies are consistent with the generation of an alkyl radical from the alkyl electrophile, as well as with reversibility for elementary steps that precede carbon-carbon bond formation (olefin binding to iron and ß-migratory insertion).

Water Activation Triggered by Cu-Co Double-Atom Catalyst for Silane Oxidation.

High-performance catalysts sufficient to significantly reduce the energy barrier of water activation are crucial in facilitating reactions that are restricted by water dissociation. Herein we present a Cu-Co double-atom catalyst (CuCo-DAC), which possesses a uniform and well-defined CuCoN6 (OH) structure, and works together to promote water activation in silane oxidation. The catalyst achieves superior catalytic performance far exceeding that of single-atom catalysts (SACs). Various functional silanes are converted into silanols with up to 98 % yield and 99 % selectivity. Kinetic studies show that the activation energy of silane oxidation by CuCo-DAC is significantly lower than that of Cu single-atom catalyst (Cu-SAC) and Co single-atom catalyst (Co-SAC). Theoretical calculations demonstrate two different reaction pathways where water splitting is the rate-determining step and it is accelerated by CuCo-DAC, whereas H2 formation is key for its single-atom counterpart.

Photo-Induced Halogen-Atom Transfer: Generation of Halide Radicals for Selective Hydrohalogenation Reactions.

The first photo-mediated process enabling the generation of halide radicals by Halogen-Atom Transfer (XAT) is described. Contrary to radical transformations involving XAT reactivity, which exploit stable carbon radicals, this unique approach uses 1,2-dihaloethanes for the generation of unstable carbon radicals by XAT. These transient radicals then undergo ß-scission with release of ethylene and formation of more stable halide radicals which have been used in selective hydrohalogenations of a large number of unsaturated hydrocarbons, including Michael acceptors, unactivated alkenes and alkynes. This hydrohalogenation is tolerant of a broad range of functionalities and is believed to proceed through a radical-chain manifold that propagates by the use of silane derivatives.

Cobalt-Catalyzed Dehydrogenative C-H Silylation of Alkynylsilanes.

Herein, we report that a cobalt catalyst permits the general synthesis of substituted alkynylsilanes through dehydrogenative coupling of alkynylsilanes and hydrosilanes. Several silylated alkynes, including di- and trisubstituted ones, were prepared in a one-step procedure. Thirty-seven compounds were synthesized for the first time by applying our catalyst system. The alkynylsilanes bearing hydrosilyl moieties provide an opportunity for further functionalization (e. g., hydrosilylation). The use of primary silanes as substrates and precatalyst activators permits the use of inexpensive and easily accessible 3d metal precatalysts, and avoids the presence of additional activators.

Electrochemical Synthesis of gem-Difluoro- and γ-Fluoro-Allyl Boronates and Silanes.

The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α-trifluoromethyl or α-difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem-difluoro and γ-fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L-1 .h-1 and 496 g.L-1 .h-1 ). Moreover, the synthetic utility of these building blocks was highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested to explain the formation of the products.

A Quick and Reproducible Silanization Method by Using Plasma Activation for Hydrophobicity-Based Kinesin Single Molecule Fluorescence-Microscopy Assays.

Single-molecule assays often require functionalized surfaces. One approach for microtubule assays renders surfaces hydrophobic and uses amphiphilic blocking agents. However, the optimal hydrophobicity is unclear, protocols take long, produce toxic waste, and are susceptible to failure. Our method uses plasma activation with hydrocarbons for hexamethyldisilazane (HMDS) silanization in the gas phase. We measured the surface hydrophobicity, its effect on how well microtubule filaments were bound to the surface, and the number of nonspecific interactions with kinesin motor proteins. Additionally, we tested and discuss the use of different silanes and activation methods. We found that even weakly hydrophobic surfaces were optimal. Our environmentally friendly method significanty reduced the overall preparation effort and resulted in reproducible, high-quality surfaces with low variability. We expect the method to be applicable to a wide range of other single-molecule assays.