Borane-dimethyl Sulfide Complex Research Articles

Polymer‐Derived Ceramic Coatings with Excellent Thermal Cycling Stability

In the present work, transition metal‐containing preceramic silicon polymers were synthesized via chemical modification of a commercially available organopolysilazane with Hf and Ta amido complexes as well as with borane dimethyl sulfide complex. The incorporation of transition metals into the polymer structure, their influence on ceramization and processability were thoroughly investigated. Moreover, the prepared preceramics were coated onto silicon wafers via spin coating and converted into crack‐free, amorphous SiHfTa(B)CN‐based ceramic coatings with excellent adhesion to the substrate. The composition of the ceramic coatings was investigated via X‐ray photoelectron spectroscopy (XPS) and their high‐temperature behavior was studied via oxidation tests performed at 1100 °C. Moreover, a thermal cycling procedure to temperatures above 1250 °C with rapid heating and cooling rates (i.e., in the range of 100–120 K s−1) was applied to the ceramic coating, which showed no damage even after ten thermal cycles, indicating their outstanding performance and their potential for use as environmental barrier coatings at high temperatures.

Atom-Economical Synthesis of Lewis Acidic Boron Containing Porous Organic Polymers via Hydroboration Polymerization for Basic Chemical Capture.

Atom economy is one of the main concerns for material synthesis. Here, the facile synthesis of Lewis acidic boron-containing porous organic polymers (B-POPs) via hydroboration polymerization reaction of commercially available borane dimethyl sulfide complex (BH3 ∙SMe2 ) with multi-alkynes under mild reaction conditions is presented. This new synthetic method for B-POPs has the advantage of high atom economy. The resulted porous alkenyl borane polymers (PABPs) have unique features such as high boron content, strong Lewis acidity, and high surface areas. Owing to the strong Lewis acid-base interactions, PABPs exhibit excellent adsorptive capacity toward triethylamine (up to 841mgg-1 ) and pyridine (up to 1396mgg-1 ) vapor.

Sequential Nitrile Amidination-Reduction as a Straightforward Procedure to Selective Linear Polyamine Preparation.

A straightforward strategy toward the efficient synthesis of linear saturated polyamines containing 1,2-diaminoethane and/or 1,3-diaminopropane fragments has been developed. The procedure is based on the chemistry of 5- and 6-membered cyclic amidines, including their efficient synthesis from nitrile precursors and subsequent chemoselective reductive-opening by a borane-dimethyl sulfide complex. This two-step procedure provides a robust methodology for the synthesis of linear polyamine skeletons under nonharsh conditions and free of using selective protective groups or tedious workups.

High Yield Autoclave Synthesis of pure M2B12H12 (M = Na, K)

Metal dodecaborates (MxB12H12) are a versatile class of materials used in polymer chemistry and cancer treatment and are promising candidates as electrolytes for solid-state batteries. However, a general and scalable approach has not yet been developed for producing high-purity B12H122- derivatives. In this work, we report a simple, efficient, and environmentally benign solvothermal method to prepare diffraction and 11B NMR pure Na2B12H12 (85% yield) and K2B12H12 (84% yield). This new synthetic approach is based on the use of the borane dimethyl sulfide complex (DMS·BH3) and borohydrides (NaBH4, KBH4) heated at different temperatures in diglyme in an autoclave. It was found that high-purity Na2B12H12·diglyme solvate is obtained via an intermediate formation of B3H8-, B9H14-, and B11H14-, which are all soluble in diglyme. Heating under vacuum is shown to be efficient for removing the coordinated diglyme, allowing the formation of unsolvated Na2B12H12. Autoclave synthesis starting from KBH4 directly yields solvent-free K2B12H12, and ball-milling KBH4 prior to the synthesis enabling us to significantly improve the final yield. The new synthetic method paves the way for large-scale synthesis of MxB12H12 derivatives, enabling to envisage a wider scope of practical applications.

Single‐source‐precursor derived bulk Si3N4/HfBxN1‐x ceramic nanocomposites with excellent oxidation resistance

AbstractIn the present work, bulk Si3N4/HfBxN1‐x ceramic nanocomposites were successfully fabricated via a polymer‐derived ceramic approach. The chemical reaction to form the single‐source precursor was confirmed by FT‐IR and XPS, in which both Si−H and N−H groups of perhydropolysilazane react with borane dimethyl sulfide complex and tetrakis(dimethylamido) hafnium(IV). The investigation of the polymer‐to‐ceramic transformation of the synthesized precursors indicates that Hf‐ and B‐modified PHPS exhibits high ceramic yields of up to 100 wt % after pyrolysis at 1000 °C under ammonia. Moreover, XRD and TEM results show that the SiHfBN ceramics with a molar ratio of B : Hf=5 and 10 resist crystallization at temperatures up to 1500 °C and separate after annealing at 1700 °C into nanocomposites comprising of an α‐Si3N4 matrix with embedded ternary HfBxN1‐x phases, solid solutions of rock salt‐type HfN and HfB. Based on the investigation, warm‐pressing was applied to fabricate bulk SiHfBN specimens, and the oxidation behavior of samples annealed at 1700 °C was recorded at 1500 °C over a range of oxidation times between 1 and 50 h. The weight changes of Si3N4/HfBxN1‐x ceramics with B : Hf molar ratios of 2 : 1, 5 : 1 and 10 : 1 are 4.31 %, 4.37 % and 2.57 %, respectively. The formation of HfSiO4, B2O3 and SiO2 during oxidation plays a crucial role for the improvement of the oxidation resistance of the Si3N4/HfBxN1‐x ceramics.

Boron-modified perhydropolysilazane towards facile synthesis of amorphous SiBN ceramic with excellent thermal stability

SiBN ceramics are widely considered to be the most promising material for microwave-transparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant. This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations. Carbon- and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors, which were subsequently pyrolyzed and annealed under N2 atmosphere (without ammonolysis) to prepare SiBN ceramics at 1100, 1200, and 1300 °C with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process. The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride. Particularly, the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si, B, and N at 1300 °C. Incorporation of boron into the Si—N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.

High‐temperature phase and microstructure evolution of polymer‐derived SiZrCN and SiZrBCN ceramic nanocomposites

ABSTRACTA zirconium and a zirconium/boron containing single‐source precursor were synthesized via chemical modification of a commercially available polysilazane (Durazane 1800) with tetrakis (dimethylamido) zirconium (IV) (TDMAZ) as well as with both TDMAZ and borane dimethyl sulfide complex, respectively. The polymer‐to‐ceramic transformation of the precursors into SiZrCN and SiZrBCN ceramics as well as the thermal evolution of their phase composition and microstructure was studied. The pyrolysis of the precursors led to the formation of amorphous SiZrCN and SiZrBCN ceramics. Interestingly, the as prepared SiZrBCN ceramic was single‐phasic and fully featureless; whereas SiZrCN exhibited the presence of nano‐sized ZrO2 particles; however, only very localized in close proximity to internal surfaces. Heat treatment at higher temperatures induced crystallization processes in both prepared ceramics. Thus, at temperatures beyond 1500°C, cubic ZrCxNy, β‐Si3N4 as well as β‐SiC were generated. It was shown that the incorporation of B into SiZrCN suppressed the crystallization of ZrCxNy and, in addition, impeded the reaction of SiNx with C, resulting in an improved thermal stability of SiZrBCN compared to SiZrCN ceramic. Moreover boron was shown to be mainly located in the sp2‐hybridized “free” carbon present in SiZrBCN, forming a turbostratic BCN phase which has been unequivocally detected by means of high‐resolution transmission electron microscopy (HRTEM) and energy‐dispersive X‐ray spectroscopy (EDS).

Continuous-Flow Amide and Ester Reductions Using Neat Borane Dimethylsulfide Complex.

Reductions of amides and esters are of critical importance in synthetic chemistry, and there are numerous protocols for executing these transformations employing traditional batch conditions. Notably, strategies based on flow chemistry, especially for amide reductions, are much less explored. Herein, a simple process was developed in which neat borane dimethylsulfide complex (BH3⋅DMS) was used to reduce various esters and amides under continuous‐flow conditions. Taking advantage of the solvent‐free nature of the commercially available borane reagent, high substrate concentrations were realized, allowing outstanding productivity and a significant reduction in E‐factors. In addition, with carefully optimized short residence times, the corresponding alcohols and amines were obtained in high selectivity and high yields. The synthetic utility of the inexpensive and easily implemented flow protocol was further corroborated by multigram‐scale syntheses of pharmaceutically relevant products. Owing to its beneficial features, including low solvent and reducing agent consumption, high selectivity, simplicity, and inherent scalability, the present process demonstrates fewer environmental concerns than most typical batch reductions using metal hydrides as reducing agents.

Reduction of Amides and Esters with Borane Dimethyl Sulfide Complex

Reduction of Amides and Esters with Borane Dimethyl Sulfide Complex

Catalytic CO2 Reduction with Boron- and Aluminum Hydrides.

The previously reported dimeric NHI aluminum dihydrides 1 a,b, as well as the bis(NHI) aluminum dihydride salt 9 +[OTs]−, the bis(NHI) boron dihydride salt 10 +[OTs]−, and the “free” bis(NHI) ligand 12 were investigated with regard to their activity as a homogenous (pre)catalyst in the hydroboration (i. e. catalytic reduction) of carbon dioxide (CO2) in chloroform under mild conditions (i. e. room temperature, 1 atm; NHI=N‐heterocyclic imine, Ts=tosyl). Borane dimethylsulfide complex and catecholborane were used as a hydride source. Surprisingly, the less sterically hindered 1 a exhibited lower catalytic activity than the bulkier 1 b. A similarly unexpected discrepancy was found with the lower catalytic activity of 10 + in comparison to the one of the bis(NHI) 12. The latter is incorporated as the ligand to the boron center in 10 +. To elucidate possible mechanisms for CO2 reduction the compounds were subjected to stoichiometric reactivity studies with the borane or CO2. Aluminum carboxylates 4, 6, and 7 + with two, four, and one formate group per two aluminum centers were isolated. Also, the boron formate salt 11 +[OTs]− was characterized. Selected metal formates were subjected to stoichiometric reactions with boranes and/or tested as a catalyst. We conclude that each type of catalyst (1 a,b, 9 +, 10 +, 12) follows an individual mechanistic pathway for CO2 reduction.

Synthesis of (+)-goniopypyrone and (+)-goniotriol using Pd-catalyzed carbonylation

Syntheses of (+)-goniopypyrone and (+)-goniotriol isolated from Goniothalamus giganteus were achieved. The key steps involve Pd-catalyzed carbonylation for lactone ring formation and diastereoselective reduction of ynone using the (R)-CBS catalyst and borane dimethyl sulfide complex.

Activation of dihydrogen by 1,4,2,5-diazadiborinine

Activation of dihydrogen (H2) by 1,4,2,5-diazadiborinine is reported. Under the heating condition, treatment of 1,4,2,5-diazadiborinine with H2 results in the cleavage of HH bond, to afford product 2, which was fully characterized by NMR and IR spectroscopy as well as X-ray diffraction and HRMS analysis. In the presence of borane dimethylsulfide complex (BH3·SMe2), 2 readily isomerizes to 3 under the mild reaction condition.

Rapid Metal‐Free Formation of Free Phosphines from Phosphine Oxides

AbstractA rapid method for the reduction of secondary phosphine oxides under mild conditions has been developed, allowing simple isolation of the corresponding free phosphines. The methodology involves the use of pinacol borane (HBpin) to effect the reduction while circumventing the formation of a phosphine borane adduct, as is usually the case with various other commonly used borane reducing agents such as borane tetrahydrofuran complex (BH3⋅THF) and borane dimethyl sulfide complex (BH3⋅SMe2). In addition, this methodology requires only a small excess of reducing agent and therefore compares favourably not just with other borane reductants that do not require a metal co‐catalyst, but also with silane and aluminium based reagents.magnified image

Synthesis of Enantioenriched Aryl‐tert‐Butylphenylphosphine Oxides via Cross‐Coupling Reactions of tert‐Butylphenylphosphine Oxide with Aryl Halides

A series of enantiomerically enriched tertiary phosphine oxides have been prepared via the Pd‐catalyzed cross‐coupling reactions of enantiomerically pure tert‐butylphenylphosphine oxide, with a variety of aryl iodides and bromides. This new protocol under optimized reaction conditions [toluene, 110 0C, Pd(PPh3)4, K2CO3 (or Et3N)] afforded highly functionalized P‐chiral phosphine oxides with a yield of 78% to 95% and with enantiomeric excesses above 98%. The stereoretentive outcome of the cross‐coupling reactions was proved by X‐ray crystallography of selected phosphine oxides: (S)‐(2‐aminophenyl)(tert‐butyl)(phenyl)phosphine oxide (3a) and (S)‐anthracen‐9‐yl(tert‐butyl)(phenyl)phosphine oxide (3i). When attempting to convert the enantiomerically pure phosphine oxide 3a to the corresponding borane by the treatment with the borane dimethyl sulfide complex partial stereoerosion at a stereogenic phosphorus atom was observed. Racemic tert‐butyl (2‐(dimethylamino)phenyl)(phenyl)phosphine (7a) was isolated in a quantitative yield upon deprotection of the corresponding borane (8a) and converted to a palladium crystalline complex (9), the structure of which has been proved by X‐ray crystallography.

Amine modified electrospun PIM-1 ultrafine fibers for an efficient removal of methyl orange from an aqueous system

Polymers of Intrinsic Microporosity (PIM-1) is a promising material for adsorption and separation applications. While PIM-1 displays high affinity for neutral species, it shows lack of interaction with charged molecules in an aqueous system due to non-polar nature of it. Functionalization of PIM-1 provides an advantage of tailoring the interaction ability as well as the adsorption performance of PIM-1 towards target pollutants. In this study, electrospun Polymer of Intrinsic Microporosity (PIM-1) fibrous membrane (PIM-FM) was reacted with borane dimethyl sulfide complex to obtain amine modified PIM-1 fibrous membrane (AM-PIM-FM). Furthermore, PIM-1 film, which is referred as PIM-1 dense membrane (PIM-DM), was also modified under the same conditions as a control material. Structural analyses have confirmed that nitrile groups of PIM-1 have been fully converted to amine group as a result of the reduction reaction. Average fiber diameter of parent PIM-1 fibers was found 2.3 ± 0.3 μm, and it remained almost the same after the amine modification. In addition, no physical damage has been observed on fiber structure based on the SEM analysis. Both amine modified PIM-1 dense and fibrous membranes became insoluble in common organic solvents. Before the modification, water contact angle of PIM-FM was 138 ± 2° which also remained almost the same after the modification, showing water contact angle of 131 ± 8°. The insolubility along with amine functionality make membranes promising materials for adsorption of anionic dyes from wastewater. Here, dye (i.e. Methyl Orange) removal ability of AM-PIM-FM from an aqueous system was investigated and compared with parent PIM-1 (PIM-FM) as well as dense membrane form (AM-PIM-DM). AM-PIM-FM shows extremely higher adsorption capacity than that of PIM-FM and AM-PIM-DM. The maximum adsorption capacity of AM-PIM-FM was found 312.5 mg g−1 for Methyl Orange. Langmuir isotherm model was found more favorable for the adsorption. AM-PIM-FM was employed effectively in continuous adsorption/desorption studies for several times without having any damage on fiber morphology using batch adsorption process. Furthermore, AM-PIM-FM was successfully used as a molecular filter for the removal of methyl orange from an aqueous system. The results indicate that AM-PIM-FM could be a promising adsorbent for removal of anionic molecules from an aqueous system.

Synthesis and characterization of zirconium diboride precursor based on polycentric bridge bonds

Zirconium diboride (ZrB2) is one of the most important ultrahigh temperature ceramics (UHTCs). ZrB2 precursor was synthesized with bis(cyclopentadienyl)zirconium dihydride (Cp2ZrH2) and borane-dimethyl sulfide complex (BH3·S(CH3)2). The influences of molar ratio of reactants and reaction temperature on the solubility of the as-synthesized precursors were investigated. The molecular structure of the precursor, pyrolysis behavior, and the composition of the derived ceramics were investigated by X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infrared Spectroscopy (FT IR), Raman Spectroscopy (RMS), 1H Nuclear Magnetic Resonance Spectroscopy (1H NMR), 11B Nuclear Magnetic Resonance Spectroscopy (11B NMR), Thermogravimetric-Mass Spectroscopy (TG-MS), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM), respectively. The results showed that, the precursor was an oligomer based on Zr–H–B polycentric bridge bonds with molecular weight of 750 and formula as (Cp2Zr(BH4)2)3. The precursor would probably further polymerize under vacuum or at high temperature and lead to an insoluble polymer. The ceramic yield of the precursor at 1000 °C was around 66% under N2 atmosphere. After pyrolyzed at 1800 °C, the derived ceramics were composed of h-ZrB2, ZrC, and free carbon with a formula as ZrB1.38C2.18.

Synthesis and characterization of zirconium diboride ceramic precursor

In the present study, ZrB2 precursor which met the requirements of polymer infiltration-pyrolysis process, was synthesized and characterized. ZrB2 precursor was synthesized with bis(cyclopentadienyl)zirconium dihydride (Cp2ZrH2), borane-dimethyl sulfide complex (BH3·S(CH3)2), and vinyltrimethylsilane ((CH3)3Si(CHCH2), VTMS). The molecular structure of the precursor, pyrolysis behavior, and the composition of the derived ceramics were investigated. The results showed that, the as-synthesized precursor was an oligomer based on Zr–H–B polycentric bridge bonds. The precursor was stable in an inert atmosphere. The ceramic yield of the precursor at 1200°C was around 65.5% under N2 atmosphere. The derived ceramics obtained under 1200°C were composed of h-ZrB2, m-ZrO2 and t-ZrO2. When the temperature was up to 1400°C, peaks of ZrC emerged due to carbothermic reduction. m-ZrO2 and t-ZrO2 disappeared with the pyrolysis temperature above 1600°C. The derived ceramics pyrolyzed at 1800°C were composed of h-ZrB2 and ZrC, and the former was the predominant phase.

Convenient and Efficient Syntheses of N 6- and N 4- Substituted Adenines and Cytosines and their 2′-Deoxyribosides

Convenient and efficient methods of the synthesis of N6- and N4-substituted derivatives of adenine and cytosine and their 2′-deoxyribosides were developed. The reactions of either unprotected nucleobases (adenine, cytosine) or unprotected 2′-deoxyribosides with aryl or alkyl aldehydes give corresponding Schiff bases that can be reduced to the target title compounds with high overall yields. In the case of aryl aldehydes the imine derivatives are obtained in the presence of methoxides in methanol and reduced with sodium borohydride. The corresponding reactions with alkyl aldehydes require the use of acetic acid and borane dimethyl sulfide complex instead.

Synthesis of Ultrahigh‐Temperature Stable Hafnium‐Containing Ceramic Nanocomposites

Polymer-derived ceramic nanocomposites (PDC-NCs) can be synthesized via thermal conversion of suitable single-source precursors, leading in a first step to amorphous single-phase ceramics, which subsequently undergo phase separation pro- cesses to furnish bi- or multiphase ceramic nanocomposites. PDC-NCs have been shown to be excellent candidate materials suitable for applications at ultrahigh-temperatures and under harsh environments. [1,2] In the present work, amorphous SiHf(B)CN-based PDC-NCs were synthesized via cross-link- ing and ceramization of a polysilazane which was chemically modified by Hf(NEt2)4 and borane dimethylsulfide complex (BH3.SMe2). High-temperature annealing of the obtained amorphous SiHf(B)CN ceramics in nitrogen atmosphere led to HfN/Si(B)CN nanocom-posites; whereas HfB2/Si(B)CN was obtained upon annealing in argon atmosphere. The presented results emphasize a convenient preparative approach to nanos- tructured ultrahigh-temperature stable materials starting from a greatly flexible/compliant single-source precursor.

Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

The selective reduction of dimethyl 3-oxoglutarate was accomplished in different levels. A high yielding sodium borohydride reduction of the keto group is fully described leading to dimethyl 3-hydroxyglutarate. When borane-dimethyl sulfide (BMS) complex was used, a diol or a triol compound can be obtained by selective or total reduction of 3-hydroxy- or 3-oxoglutarate, respectively, allowing an efficient and practical route to 1,3,5-oxygenated compounds.