40391-85-3

Upstream product

• 67-56-1 methanol 
• 775-12-2 diphenylsilane 
• 916501-34-3 2,2-diphenyl-1,1,3,3-tetramethyl-1,2,3-trisilacycloheptane 
• 84960-82-7 diphenylsilylene 
• 17950-94-6 dideuteriodiphenylsilane 
• 6843-66-9 dimethoxy(diphenyl)silane 
• 1111-72-4 carbon dioxide 
• 1000206-70-1 1,1,3,3-tetramethyl-2,2-diphenyl-1,2,3-trisilacyclohexane 
• 1072-43-1 propylene sulphide 

Downstream Products

• 53668-78-3 chloromethoxydiphenylsilane 
• 312-40-3 difluorodiphenylsilane 
• 6843-66-9 dimethoxy(diphenyl)silane 

Relevant academic research and scientific papers

POP-pincer silyl complexes of group 9: Rhodium versus iridium

9,9-Dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(P iPr2)2) derivatives RhCl{xant(P iPr2)2} (1) and IrHCl{xant(PiPr 2)[iPrPCH(Me)CH2]} (2) react with diphenylsilane and triethylsilane to give the saturated d6-compounds RhHCl(SiR3){xant(PiPr2)2} (SiR 3 = SiHPh2 (3), SiEt3 (4)) and IrHCl(SiR 3){xant(PiPr2)2} (SiR3 = SiHPh2 (5), SiEt3 (6)). Complexes 3 and 5 undergo a Cl/H position exchange process via the MH{xant(PiPr2) 2} (M = Rh (8), Ir (E)) intermediates. The rhodium complex 3 affords the square planar d8-silyl derivative Rh(SiClPh2) {xant(PiPr2)2} (7), whereas the iridium derivative 5 gives IrH2(SiClPh2){xant(PiPr 2)2} (9), which is stable. In agreement with the formation of 7, the reactions of 8 with silanes are a general method to prepare square planar d8-rhodium-silyl derivatives. Thus, the addition of triethylsilane and triphenylsilane to 8 initially leads to the dihydrides RhH2(SiR3){xant(PiPr2)2} (SiR3 = SiEt3 (10), SiPh3 (11)), which lose molecular hydrogen to afford Rh(SiR3){xant(PiPr 2)2} (SiR3 = SiEt3 (12), SiPh 3 (13)). Treatment of 7 with NaBArF4· 2H2O leads to the cationic five-coordinate d6-species [RhH{Si(OH)Ph2}{xant(PiPr2)2}] BArF4 (14) through a silylene intermediate. According to the participation of the latter in the formation of 14, this cation is an efficient catalyst precursor for the monoalcoholysis of diphenylsilane with a wide range of alcohols, reaching turnover frequencies at 50% of conversion between 4000 and 76 500 h-1. The X-ray structures of 3, 6, 7, 9, 12, and 14 are also reported.

Self-Assembled Open Porous Nanoparticle Superstructures

Imparting porosity to inorganic nanoparticle assemblies to build up self-assembled open porous nanoparticle superstructures represents one of the most challenging issues and will reshape the property and application scope of traditional inorganic nanoparticle solids. Herein, we discovered how to engineer open pores into diverse ordered nanoparticle superstructures via their inclusion-induced assembly within 1D nanotubes, akin to the molecular host-guest complexation. The open porous structure of self-assembled composites is generated from nonclose-packing of nanoparticles in 1D confined space. Tuning the size ratios of the tube-to-nanoparticle enables the structural modulation of these porous nanoparticle superstructures, with symmetries such as C1, zigzag, C2, C4, and C5. Moreover, when the internal surface of the nanotubes is blocked by molecular additives, the nanoparticles would switch their assembly pathway and self-assemble on the external surface of the nanotubes without the formation of porous nanoparticle assemblies. We also show that the open porous nanoparticle superstructures can be ideal candidate for catalysis with accelerated reaction rates.

Carbon dioxide hydrosilylation to methane catalyzed by zinc and other first-row transition metal salts

We accomplished zinc catalyzed hydrosilylation of carbon dioxide (CO2) to silyl formate (C+II), bis(silyl)acetal (C0), methoxysilane (C1II), and finally methane (C1IV). Among several zinc salts, we found that Zn(OAc)2 with ligand 1,10-phenanthroline was the best. A turnover number of 815000 was achieved using the zinc catalyst to yield C+II. Unexpectedly, we observed the generation of CO from CO2 and hydrosilane for the first time. In addition to Zn, other first-row transition metals (Mn, Fe, Co, Ni, and Cu) also served as Lewis acid catalysts for CO2 hydrosilylation, regardless of the nature of the metal.

Synthesis of hydrosilanes: Via Lewis-base-catalysed reduction of alkoxy silanes with NaBH4

Hydrosilanes were synthesized by reduction of alkoxy silanes with BH3 in the presence of hexamethylphosphoric triamide (HMPA) as a Lewis-base catalyst. The reaction was also achieved using an inexpensive and easily handled hydride source NaBH4, which reacted with EtBr as a sacrificial reagent to form BH3in situ.

Zerovalent Nickel Compounds Supported by 1,2-Bis(diphenylphosphino)benzene: Synthesis, Structures, and Catalytic Properties

Zerovalent nickel compounds which feature 1,2-bis(diphenylphosphino)benzene (dppbz) were obtained via the reactivity of dppbz towards Ni(PMe3)4, which affords sequentially (dppbz)Ni(PMe3)2 and Ni(dppbz)2. Furthermore, the carbonyl derivatives (dppbz)Ni(PMe3)(CO) and (dppbz)Ni(CO)2 may be obtained via the reaction of CO with (dppbz)Ni(PMe3)2. Other methods for the synthesis of these carbonyl compounds include (i) the formation of (dppbz)Ni(CO)2 by the reaction of Ni(PPh3)2(CO)2 with dppbz and (ii) the formation of (dppbz)Ni(PMe3)(CO) by the reaction of (dppbz)Ni(CO)2 with PMe3. Comparison of the ν(CO) IR spectroscopic data for (dppbz)Ni(CO)2 with other (diphosphine)Ni(CO)2 compounds provides a means to evaluate the electronic nature of dppbz. Specifically, comparison with (dppe)Ni(CO)2 indicates that the o-phenylene linker creates a slightly less electron donating ligand than does an ethylene linker. The steric impact of the dppbz ligand in relation to other diphosphine ligands has also been evaluated in terms of its buried volume (%Vbur) and steric maps. The nickel center of (dppbz)Ni(PMe3)2 may be protonated by formic acid at room temperature to afford [(dppbz)Ni(PMe3)2H]+, but at elevated temperatures, effects catalytic release of H2 from formic acid. Analogous studies with Ni(dppbz)2 and Ni(PMe3)4 indicate that the ability to protonate the nickel centers in these compounds increases in the sequence Ni(dppbz)2 3)2 3)4; correspondingly, the pKa values of the protonated derivatives increase in the sequence [Ni(dppbz)2H]+ 3)2H]+ 3)4H]+. (dppbz)Ni(PMe3)2 and Ni(PMe3)4 also serve as catalysts for the formation of alkoxysilanes by (i) hydrosilylation of PhCHO by PhSiH3 and Ph2SiH2 and (ii) dehydrocoupling of PhCH2OH with PhSiH3 and Ph2SiH2.

Carbon Dioxide Reduction to Methanol Catalyzed by Mn(I) PNP Pincer Complexes under Mild Reaction Conditions

Well-defined Mn(I) hydrido carbonyl PNP pincer-type complexes were tested as efficient and selective nonprecious transition metal catalysts for the reduction of CO2 to MeOH in the presence of hydrosilanes. The choice of reaction temperature and

Synthesis of nitrogen and sulfur co-doped hierarchical porous carbons and metal-free oxidative coupling of silanes with alcohols

Hierarchically porous N and S co-doped carbon was prepared by using 2,5-dihydroxy-1,4-benzoquinone as the carbon source, thiourea as the N and S source, and SiO2 particles as the template. Using the material as the catalyst, oxidative coupling of silanes with alcohols was conducted for the first time under metal-free conditions.

Using the nonaqueous electrolytic solution and secondary battery

PROBLEM TO BE SOLVED: To provide nonaqueous electrolyte solution capable of improving at least either large-current charge/discharge characteristics or charge/discharge capacity, and a nonaqueous electrolyte solution secondary battery using it. SOLUTION: Electrolyte solution that is liquid electrolyte is immersed in a separator 23. The electrolyte solution contains a liquid solvent, for instance, a nonaqueous solvent such as an organic solvent, and electrolyte salt dissolved in the nonaqueous solvent. Further, as additives, it contains at least one type selected from tris (penta-fluorophenyl) borane (TPFPB) and tris-borate (2H-hexafluoro isopropyl) (THFPB), and at least one type selected from vinylene carbonate (VC) and vinyl ethylene carbonate (VEC). COPYRIGHT: (C)2008,JPO&INPIT

Silanones and silanethiones from the reactions of transient silylenes with oxiranes and thiiranes in solution. The direct detection of diphenylsilanethione

The transient silylenes SiMe2 and SiPh2 react with cyclohexene oxide (CHO), propylene oxide (PrO), and propylene sulfide (PrS) in hydrocarbon solvents to form products consistent with the formation of the corresponding transient silanones and silanethiones, respectively. Laser flash photolysis studies show that these reactions proceed via multistep sequences involving the intermediacy of the corresponding silylene-oxirane or -thiirane complexes, which are formed with rate constants close to the diffusion limit in all cases and exhibit UV absorption spectra similar to those of the corresponding complexes with the nonreactive O- and S-donors, tetrahydrofuran and tetrahydrothiophene. The SiMe2-PrO and SiPh2-PrO complexes both exhibit lifetimes of ca. 300 ns, and are longer-lived than the corresponding complexes with CHO, which are both in the range of 230-240 ns. On the other hand, the silylene-PrS complexes are considerably shorter-lived and vary with silyl substituent; the SiMe2-PrS complex decays with the excitation laser pulse (i.e., τ ≥ 25 ns), while the SiPh2-PrS complex exhibits τ = 48 ± 3 ns. The decay of the SiPh2-PrS complex affords a long-lived transient product exhibiting λ max ≈ 275 nm, which has been assigned to diphenylsilanethione (Ph2Si=S) on the basis of its second order decay kinetics and absolute rate constants for reaction with methanol, tert-butanol, acetic acid, and n-butyl amine, for which values in the range of 1.4 × 108 to 3.2 × 109 M-1 s-1 are reported. The experimental rate constants for decay of the SiMe2-epoxide and -PrS complexes indicate free energy barriers (ΔG?) of ca. 8.5 and ≥7.1 kcal mol-1 for the rate-determining steps leading to dimethylsilanone and -silanethione, respectively, which are compared to the results of DFT (B3LYP/6-311+G(d,p)) calculations of the reactions of SiH 2 and SiMe2 with oxirane and thiirane. The calculations predict a stepwise C-O cleavage mechanism involving singlet biradical intermediates for the silylene-oxirane complexes, and a concerted mechanism for silanethione formation from the silylene-thiirane complexes, in agreement with earlier ab initio studies of the SiH2-oxirane and -thiirane systems.

Kinetics and mechanisms of the reactions of transient silylenes with amines

The N-H insertion reactions of dimethyl-, diphenyl-, and dimesitylsilylene (SiMe2, SiPh2, and SiMes2, respectively) with n-butylamine (BuNH2) and diethylamine (Et2NH) were studied in hexanes by steady-state and laser photolysis methods. The process begins with the formation of the corresponding Lewis acid-base complexes, which decayed with second-order kinetics at rates that show modest sensitivity to silylene and amine structures. The complexation process, which was also studied using triethylamine (Et3N), proceeds at rates close to the diffusion limit, but the rate constants vary systematically with steric bulk in the amine. Equilibrium constants were determined for the complexation of Et2NH and Et3N with SiMes2, which proceeds reversibly. The complexes of SiMe2 and SiPh2 with BuNH2 and Et2NH decayed with pseudo-first-order rate coefficients in the 104-105s-1 range. This is consistent with upper limits of about 106M-1s-1 for the rate constants for amine-catalyzed H-migration, which is thought to be the dominant mechanism for product formation from the complexes. The results are compared to published kinetic data for the O-H insertion reactions of these silylenes with alcohols, which also proceeds via initial complexation followed by catalytic proton transfer. The results indicate that catalyzed H-transfer in the amine complexes is at least 104 times slower than the analogous process in silylene-MeOH complexes. The experimental data are compared to the results of theoretical calculations of the SiMe2+NH2Me and SiMe 2+MeOH potential energy surfaces, carried out at the Gaussian-4 and B3LYP/6-311+G(d,p) levels of theory.