76111-01-8

Upstream product

• 100-42-5 styrene 
• 760-32-7 diethylmethylsilane 

Relevant academic research and scientific papers

High catalytic activity and selectivity in hydrosilylation of new Pt(II) metallosupramolecular complexes based on ambidentate ligands

Two new air- and water-stable Pt(II) metallosupramolecular complexes based on ambidentate ligands have been designed, synthesized and fully characterized. The structure of complexes has been determined by various analytical techniques including NMR spectroscopy and TOF-MS. Additionally, the single crystal structure of 2 was determined by X-ray diffraction. The catalytic activity of these complexes in hydrosilylation has been investigated, establishing that both have similar high activity and selectivity within a broad scope of structurally distinct olefins and hydrosilanes.

Highly efficient B(C6F5)3-catalyzed hydrosilylation of olefins

A convenient and highly efficient method for the Lewis acid-catalyzed trans-selective hydrosilylation of alkenes has been developed. The mechanism of this novel protocol operates via direct addition of silylium type species across C=C bond followed by trapping of the resultant carbenium ion with boron-bound hydride. A number of diversely substituted silanes possessing both aryl and alkyl groups at silicon atom were efficiently prepared using this hydrosilylation methodology. The possibility to employ aryl-containing hydrosilanes in this reaction opens broad capabilities for the synthesis of alcohols via a trans-selective hydrosilylation/Tamao - Fleming oxidation sequence, complementary to the existing cis-selective hydroboration/oxidation protocol.

The effect of solvents on hydrosilylation of phenylalkenes catalysed by 3>

Hydrosilylation of styrene, 2-phenyl-1-propene and trans-1-phenyl-1-propene by trialkylsilicon hydrides of the type CH3R2SiH (R = C2H5, i-C3H7, i-C4H9) catalysed by 3> in the presence of benzene, 1,3,5-triethylbenzene, 1,2,3,4-tetraethylbenzene, pentaethylbenzene, hexaethylbenzene, 1,2,3,4-tetrahydronaphthalene, cyclohexane, tetrahydrofuran (THF), tributylphosphate (TBP), dimethylacetamide (DMA), trimethylphosphate (TMP), tributylphosphate (TBP) and hexamethylphosphorictriamide (HMPA) has been studied both in anaerobic conditions and in the presence of air oxygen.Aromatic solvents were found to affect the composition of reaction products similarly as benzene.The use of THF, TBF, TMP, DMA and HMPA as solvents for hydrosilylation of styrene by the above silanes suppresses formation of the α-adduct when the reaction is carried out under unaerobic conditions.The yields of hydrosilylation of 2-phenyl-1-propene and trans-1-phenyl-1-propene by CH3(C2H5)2SiH are decreased by the addition of THF, TBP, TMP and DMA while they are increased by using HMPA as the solvent.

STERIC EFFECTS IN HYDROSILYLATION OF STYRENE

Hydrosilylation of styrene, 2-phenyl-1-propene, trans-1-phenyl-1-propene by (CH3)R2SiH (R=C2H5, i-C3H7, i-C4H9) and R3'SiH (R'=i-C3H7, t-C4H9) in the presence of 3> (I), 2> (II) and H2PtCl6 as catalysts has been studied.The reaction of styrene with (CH3)R2SiH catalysed by complex I in benzene leads to α- and β-adduct as well as to a substitution product.Analogous addition of (i-C3H7)3SiH catalysed by complexes I and II produces selectively trans-1-triisopropylsilyl-2-phenylethylene.Reaction of 2-phenyl-1-propene with CH3(C2H5)2SiH gives 1-diethylmethylsilyl-2-phenylpropane, 1-diethylmethylsilyl-2-phenyl-2-propene and 1-diethylmethylsilyl-2-phenyl-1-propene.Hydrosilylation of trans-1-phenyl-1-propene by diethylmethylsilane catalysed by complex I gave 1-diethylmethylsilyl-2-phenylpropane and 3-diethylmethylsilyl-1-phenylpropane.Conversion of 2-phenyl-1-propene and trans-1-phenyl-1-propene in their reaction with diethylmethylsilane catalysed by complex I was found to be much lower compared to the reaction with styrene and attained maximum at 60 deg C.The selectivity and rates of above reactions can be influenced by the presence of air oxygen.