772-64-5

Upstream product

• 100-42-5 styrene 
• 917-64-6 methyl magnesium iodide 
• 940-41-0 1-phenyl-2-(trichlorosilyl)ethane 
• 772-65-6 (2-phenylethyl)methyldichlorosilane 
• 75-16-1 methylmagnesium bromide 
• 591-51-5 phenyllithium 
• 754-05-2 ethenyltrimethylsilane 
• 993-07-7 trimethylsilan 
• 19372-00-0 1-(trimethylsilyl)-2-phenylethene 
• 75-77-4 chloro-trimethyl-silane 
• 17376-04-4 2-phenethyl iodide 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 60-12-8 2-phenylethanol 
• 2170-06-1 1-Phenyl-2-(trimethylsilyl)acetylene 

Downstream Products

• 100-42-5 styrene 
• 420-56-4 trimethylsilyl fluoride 
• 519-73-3 triphenylmethane 
• 52000-50-7 3-Oxo-3-[4-(2-trimethylsilanyl-ethyl)-phenyl]-propionic acid ethyl ester 
• 17146-08-6 dimethyl(2-phenylethyl)chlorosilane 
• 27490-51-3 (3,3-Dichloro-2-phenyl-propyl)-trimethyl-silane 

Relevant academic research and scientific papers

Reactivity of (bi-Oxazoline)organonickel Complexes and Revision of a Catalytic Mechanism

Bi-Oxazoline (biOx) has emerged as an effective ligand framework for promoting nickel-catalyzed cross-coupling, cross-electrophile coupling, and photoredox-nickel dual catalytic reactions. This report fills the knowledge gap of the organometallic reactivity of (biOx)Ni complexes, including catalyst reduction, oxidative electrophile activation, radical capture, and reductive elimination. The biOx ligand displays no redox activity in (biOx)Ni(I) complexes, in contrast to other chelating imine and oxazoline ligands. The lack of ligand redox activity results in more negative reduction potentials of (biOx)Ni(II) complexes and accounts for the inability of zinc and manganese to reduce (biOx)Ni(II) species. On the basis of these results, we revise the formerly proposed “sequential reduction” mechanism of a (biOx)Ni-catalyzed cross-electrophile coupling reaction by excluding catalyst reduction steps.

Electrochemical Hydrogenation with Gaseous Ammonia

As a carbon-free and sustainable fuel, ammonia serves as high-energy-density hydrogen-storage material. It is important to develop new reactions able to utilize ammonia as a hydrogen source directly. Herein, we report an electrochemical hydrogenation of alkenes, alkynes, and ketones using ammonia as the hydrogen source and carbon electrodes. A variety of heterocycles and functional groups, including for example sulfide, benzyl, benzyl carbamate, and allyl carbamate were well tolerated. Fast stepwise electron transfer and proton transfer processes were proposed to account for the transformation.

Bis(bipyridine) ruthenium(ii) bis(phosphido) metalloligand: Synthesis of heterometallic complexes and application to catalytic (E)-selective alkyne semi-hydrogenation

The first phosphido derivative of the bis(bipyridine) ruthenium(ii) fragment, cis-[(bpy)2Ru(PPh2)2] ([RuP2]), has been developed and applied as a P-donor metalloligand to form new Ru-Rh, Ru-Ir and Ru2Cu2 heterometallic complexes. The Ru-Ir hydride complex [([RuP2])IrH(NCMe)3][BF4]2 exhibits significant catalytic activity for (E)-selective semi-hydrogenation of alkynes.

Recyclable cobalt(0) nanoparticle catalysts for hydrogenations

The search for new hydrogenation catalysts that replace noble metals is largely driven by sustainability concerns and the distinct mechanistic features of 3d transition metals. Several combinations of cobalt precursors and specific ligands in the presence of reductants or under high-thermal conditions were reported to provide active hydrogenation catalysts. This study reports a new method of preparation of small, monodisperse Co(0) nanoparticles (3-4 nm) from the reduction of commercial CoCl2 in the absence of ligands or surfactants. High catalytic activity was observed in hydrogenations of alkenes, alkynes, imines, and heteroarenes (2-20 bar H2). The magnetic properties enabled catalyst separation and multiple recyclings.

Hydrosilane synthesis via catalytic hydrogenolysis of halosilanes using a metal-ligand bifunctional iridium catalyst

Hydrogenolysis of various halosilanes was catalysed by iridium amido complexes to produce hydrosilanes. Selective monohydrogenolysis of di- and trichlorosilanes similarly proceeded, resulting in the formation of chlorohydrosilanes (R2SiHCl or RSiHCl2) as synthetically important building blocks for various organosilicon compounds. A mechanistic study supported the in-situ formation of an iridium hydride species as a key intermediate, which could transfer the hydride to the silicon atom through a metal–ligand bifunctional mechanism. One-pot hydrotrimethylsilylation of olefins was achieved via successive hydrogenolysis and hydrosilylation reactions starting from Me3SiCl.

Cyclohexa-1,3-diene-based dihydrogen and hydrosilane surrogates in B(C6F5)3-catalysed transfer processes

The cyclohexa-1,3-diene motif is introduced as an equally effective alternative to the cyclohexa-1,4-diene platform in B(C6F5)3-catalysed transfer processes. The transfer hydrogenation of alkenes is realised with α-terpinene and the related transfer hydrosilylation is achieved with 5-trimethylsilyl-substituted cyclohexa-1,3-diene. Both yields and substrate scope are comparable with the prior systems.

Decamethyltitanocene hydride intermediates in the hydrogenation of the corresponding titanocene-(η2-ethene) or (η2-alkyne) complexes and the effects of bulkier auxiliary ligands

1H NMR studies of reactions of titanocene [Cp?2Ti] (Cp? = η5-C5Me5) and its derivatives [Cp?(η5:η1-C5Me4CH2)TiMe] and [Cp?2Ti(η2-CH2CH2)] with excess dihydrogen at room temperature and pressures lower than 1 bar revealed the formation of dihydride [Cp?2TiH2] (1) and the concurrent liberation of either methane or ethane, depending on the organometallic reactant. The subsequent slow decay of 1 yielding [Cp?2TiH] (2) was mediated by titanocene formed in situ and controlled by hydrogen pressure. The crystalline products obtained by evaporating a hexane solution of fresh [Cp?2Ti] in the presence of hydrogen contained crystals having either two independent molecules of 1 in the asymmetric part of the unit cell or cocrystals consisting of 1 and [Cp?2Ti] in a 2:1 ratio. Hydrogenation of alkyne complexes [Cp?2Ti(η2-R1CCR2)] (R1 = R2 = Me or Et) performed at room temperature afforded alkanes R1CH2CH2R2, and after removing hydrogen, 2 was formed in quantitative yields. For alkyne complexes containing bulkier substituent(s) R1 = Me or Ph, R2 = SiMe3, and R1 = R2 = Ph or SiMe3, successful hydrogenation required the application of increased temperatures (70-80 °C) and prolonged reaction times, in particular for bis(trimethylsilyl)acetylene. Under these conditions, no transient 1 was detected during the formation of 2. The bulkier auxiliary ligands η5-C5Me4tBu and η5-C5Me4SiMe3 did not hinder the addition of dihydrogen to the corresponding titanocenes [(η5-C5Me4tBu)2Ti] and [(η5-C5Me4SiMe3)2Ti] yielding [(η5-C5Me4tBu)2TiH2] (3) and [(η5-C5Me4SiMe3)2TiH2] (4), respectively. In contrast to 1, the dihydride 4 did not decay with the formation of titanocene monohydride, but dissociated to titanocene upon dihydrogen removal. The monohydrides [(η5-C5Me4tBu)2TiH] (5) and [(η5-C5Me4SiMe3)2TiH] (6) were obtained by insertion of dihydrogen into the intramolecular titanium-methylene σ-bond in compounds [(η5-C5Me4tBu)(η5:η1-C5Me4CMe2CH2)Ti] and [(η5-C5Me4SiMe3)(η5:η1-C5Me4SiMe2CH2)Ti], respectively. The steric influence of the auxiliary ligands became clear from the nature of the products obtained by reacting 5 and 6 with butadiene. They appeared to be the exclusively σ-bonded η1-but-2-enyl titanocenes (7) and (8), instead of the common π-bonded derivatives formed for the sterically less congested titanocenes, including [Cp?2Ti(η3-(1-methylallyl))] (9). The molecular structure optimized by DFT for compound 1 acquired a distinctly lower total energy than the analogously optimized complex with a coordinated dihydrogen [Cp?2Ti(η2-H2)]. The stabilization energies of binding the hydride ligands to the bent titanocenes were estimated from counterpoise computations; they showed a decrease in the order 1 (-132.70 kJ mol-1), 3 (-121.11 kJ mol-1), and 4 (-112.35 kJ mol-1), in accordance with the more facile dihydrogen dissociation.

Alkyne Semihydrogenation with a Well-Defined Nonclassical Co-H2 Catalyst: A H2 Spin on Isomerization and E-Selectivity

The reactivity of a CoI-H2 complex was extended toward the semihydrogenation of internal alkynes. Under ambient temperatures and moderate pressures of H2, a broad scope of alkynes were semihydrogenated using a CoI-N2 precatalyst, resulting in the formation of trans-alkene products. Furthermore, mechanistic studies using 1H, 2H, and para-hydrogen induced polarization (PHIP) transfer NMR spectroscopy revealed cis-hydrogenation of the alkyne occurs first. The Co-mediated alkene isomerization afforded the E-selective products from a broad group of alkynes with good yields and E/Z selectivity.

Use of cyclohexa-2,5-dien-1-yl-silanes as precursors for gaseous hydrosilanes

The invention relates to the use of cyclohexa-2,5-dien-1-yl-silanes of general formula I for generation of hydrosilanes in solution using a strong Lewis acid. This way, e.g., alkenes can be hydrosilylated in good yields using the cyclohexa-2,5-dien-1-yl-silanes of general formula I as transfer hydrosilylating agents in the presence of a strong Lewis acid as catalyst with concomitant formation of an arene solvent.

USE OF CYCLOHEXA-2,5-DIEN-1-YL-SILANES AS PRECURSORS FOR GASEOUS HYDROSILANES

The invention relates to the use of cyclohexa-2,5-dien-1 -yl-silanes of general formula (I), for generation of hydrosilanes in solution using a strong Lewis acid. This way, e.g., alkenes or carbonyl compounds can be hydrosilylated in good yields using the cyclohexa-2,5-dien-1 - yl-silanes of general formula I as transfer hydros! lylating agents in the presence of a strong Lewis acid as catalyst with concomitant formation of an arene solvent.