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Upstream product

• 100-42-5 styrene 
• 617-86-7 triethylsilane 
• 4545-21-5 acetophenone p-toluenesulfonylhydrazone 
• 98-86-2 acetophenone 
• 6655-35-2 Acetophenone o-nitrophenylsulfonylhydrazone 

Relevant academic research and scientific papers

Palladium(0)-catalyzed C(sp3)-Si bond formation: Via formal carbene insertion into a Si-H bond

Pd(0)-Catalyzed formal carbene insertion into Si-H bonds has been achieved as an efficient method for C(sp3)-Si bond formation. The reaction, which uses readily available N-tosylhydrazones as the diazo precursors, is highly efficient and shows a wide substrate scope. Rh(ii) and Cu(i) salts, which are the widely used catalysts for carbene insertion reactions, have been proved to be ineffective for the current reaction. A Pd(ii) carbene migratory insertion/reductive elimination mechanism is proposed.

Silver(i)-promoted insertion into X-H (X = Si, Sn, and Ge) bonds with N-nosylhydrazones

Silver(i)-promoted carbene insertion into X-H (X = Si, Sn, and Ge) bonds has been realized by using unstable diazo compounds, which are generated in situ from N-nosylhydrazones as carbene precursors. The reaction tolerates a wide range of functional groups and delivers a number of valuable silicon-containing compounds in very high yields (up to 96%). Moreover, organostannanes and organogermanes were as well effectively obtained in very good yields under optimal conditions.

NICKEL COMPLEX COMPOUND, CATALYST COMPOSITION, AND PRODUCTION METHOD OF ORGANIC SILICON COMPOUND

PROBLEM TO BE SOLVED: To provide a novel compound, especially a compound utilizable as a catalyst for a hydrosilylation reaction of alkenes or alkynes, or the like. SOLUTION: A novel nickel complex having a η3-allyl ligand having a substituent

Catalytic study of heterobimetallic rhodium complexes derived from partially alkylated s-indacene in dehydrogenative silylation of olefins

This work describes the catalytic study of heterobimetallic rhodium compounds derived from partially alkylated s-indacene in dehydrogenative silylation of olefins in order to elucidate as much as possible the effects of: solvent, temperature, chemical substrates, olefin effect, silane effect, and secondary metallic fragment. The rhodium complexes, anti-[Cp*Fe-s- Ic′-Rh(COD)] 1, anti-[Cp*Ru-s-Ic′-Rh(COD)] 2, and syn-[Cp*Ru-s-Ic′-Rh(COD)] 2′ (with s-Ic′: 2,6-diethyl-4,8-dimethyl-s-indaceneiide) were previously synthesized and characterized, and were compared with the catalytic activity of the complexes previously reported; monometallic [(COD)Rh-s-Ic′H] 3, and homobimetallic anti-[{(COD)Rh}2-s-Ic′] 4, and syn-[{(COD)Rh} 2-s-Ic′] 4′. The heterobimetallic complexes show a high activity and selectivity for the dehydrogenative silylation of styrene and these complexes show also the presence of a cooperative effect between both metallic centers, which is evidenced when compared with monometallic complex.

Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene

A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.

Synthesis of rhodium N-heterocyclic carbene complexes and their catalytic activity in the hydrosilylation of alkenes in ionic liquid medium

Rhodium complexes bearing N-heterocyclic carbene (NHC) ligands were prepared from bis(η4-1,5-cyclooctadiene) dichlorodirhodium and 1-alkyl-3-methylimidazolium-2-carboxylate, and the catalytic properties of rhodium complexes prepared in the hydrosilylation of alkenes in ionic liquid media were investigated. It was found that both the catalytic activity and selectivity of the rhodium complexes bearing NHC ligands were influenced by the attached substituents of the imidazolium cation. Additionally, rhodium complexes bearing NHC ligands in ionic liquid BMimPF6 could be reused without noticeable loss of catalytic activity and selectivity.

Comparison of structure and reactivity of phosphine-amido and hemilabile phosphine-amine chelates of rhodium

A series of mono- and binuclear rhodium(I) complexes bearing ortho-phosphinoanilido and ortho-phosphinoaniline ligands has been synthesized. Reactions of the protic monophosphinoanilines, Ph2PAr or PhPAr 2 (Ar = o-C6H4NHMe), with 0.5 equiv of [Rh(μ-OMe)(COD)]2 result in the formation of the neutral amido complexes, [Rh(COD)(P,N-Ph2PAr-)] or [Rh(COD)(P,N- PhP(Ar-)Ar)] (Ar- = o-C6H4NMe -), respectively, through stoichiometrically controlled deprotonation of an amine by the internal methoxide ion. Similarly, the binuclear complex, [Rh2(COD)2(μ-P,N,P′,N′-mapm2-)] (mapm2- = Ar(Ar-)PCH2P(Ar-)Ar), can be prepared by reaction of the protic diphosphinoaniline, mapm (Ar 2PCH2PAr2), with 1 equiv of [Rh(μ-OMe)(COD)]2. An analogous series of hemilabile phosphine-amine compounds can be generated by reactions of monophosphinoanilines, Ph2PAr′ or PhPAr′2 (Ar′ = o-C6H4NMe2), with 1 equiv of [Rh(NBD)2][BF4] to generate [Rh(NBD)(P,N-Ph 2PAr′)][BF4] or [Rh(NBD)(P,N- PhPAr′2)][BF4], respectively, or by reactions of diphosphinoanilines, mapm or dmapm (Ar′2PCH 2PAr′2), with 2 equiv of the rhodium precursor to generate [Rh2(NBD)2(μ-P,N,P′,N′-mapm)] [BF4]2 or [Rh2(NBD)2(μ-P,N, P′,N′-dmapm)][BF4]2, respectively. Displacement of the diolefin from [Rh(COD)(P,N-Ph2PAr-)] by 1,2-bis(diphenylphosphino)ethane (dppe) yields [Rh(P,P′-dppe)(P,N- Ph2PAr-)] which, while unreactive to H2, reacts readily and irreversibly with oxygen to form the peroxo complex, [RhO 2(P,P′-dppe)(P,N-Ph2PAr-)], and with iodomethane to yield [RhI(CH3)(P,P′-dppe)(P,N-Ph 2PAr-)]. Hemilabile phosphine-amine compounds can also be prepared by reactions of [Rh(P,P′-dppe)(P,N-Ph2PAr -)] with Me3OBF4 or HBF4? Et2O, resulting in (thermodynamic) additions at nitrogen to form [Rh(P,P′-dppe)(P,N-Ph2PAr′)][BF4] or [Rh(P,P′-dppe)(P,N-Ph2PAr)][BF4], respectively. The nonlabile phosphine-amido and hemilabile phosphine-amine complexes were tested as catalysts for the silylation of styrene. The amido species do not require the use of solvents in reaction media, can be easily removed from product mixtures by protonation, and appear to be more active than their hemilabile, cationic congeners. Reactions catalyzed by either amido or amine complexes favor dehydrogenative silylation in the presence of excess olefin, showing modest selectivities for a single vinylsilane product. The binuclear complexes, which were prepared in an effort to explore possible catalytic enhancements of reactivity due to metal-metal cooperativity, are in fact somewhat less active than mononuclear species, discounting this possibility.

New Rh derivatives of s-indacene active in dehydrogenative silylation of styrene

The mono- and bimetallic complexes [(2,6-diethyl-4,8-dimethyl-s-indacenide){Rh(COD)}] (1), anti-[(2,6-diethyl-4,8-dimethyl-s-indacenediide){Rh(COD)}2] (2a), syn-[(2,6-diethyl-4,8-dimethyl-s-indacenediide){Rh(COD)}2] (2b) were synthes

Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene) catalyst

A highly active and selective in situ formed platinum(N-heterocyclic carbene) catalyst for the hydrosilylation of styrene with triethylsilane is described, which unlike all other known hydrosilylation catalysts, selectively yields hydrosilylation products, but (almost) no dehydrogenative silylation products.