18816-18-7

Upstream product

• 1631-83-0 diphenylsilyl chloride 
• 185988-02-7 1,3-Difluoro-1,1,2,2,3,3-hexaphenyl-trisilane 
• 775-12-2 diphenylsilane 
• 1770-54-3 decaphenylcyclopentasilane 
• 4098-89-9 octaphenyltrisilane 

Downstream Products

• 15288-61-6 1,3-dichlorohexaphenyltrisilane 
• 139599-22-7 1,3-Diiodo-1,1,2,2,3,3-hexaphenyl-trisilane 

Relevant academic research and scientific papers

Hydrogenolysis of Polysilanes Catalyzed by Low-Valent Nickel Complexes

The dehydrogenation of organosilanes (RxSiH4?x) under the formation of Si?Si bonds is an intensively investigated process leading to oligo- or polysilanes. The reverse reaction is little studied. To date, the hydrogenolysis of Si?Si bonds requires very harsh conditions and is very unselective, leading to multiple side products. Herein, we describe a new catalytic hydrogenation of oligo- and polysilanes that is highly selective and proceeds under mild conditions. New low-valent nickel hydride complexes are used as catalysts and secondary silanes, RR′SiH2, are obtained as products in high purity.

Si-H bond activation at {(NHC)2Ni0} leading to hydrido silyl and bis(silyl) complexes: A versatile tool for catalytic Si-H/D exchange, acceptorless dehydrogenative coupling of hydrosilanes, and hydrogenation of disilanes to hydrosilanes

The unique reactivity of the nickel(0) complex [Ni2(iPr 2Im)4(COD)] (1) (iPr2Im = 1,3-di-isopropyl- imidazolin-2-ylidene) towards hydrosilanes in stoichiometric and catalytic reactions is reported. A series of nickel hydrido silyl complexes cis-[Ni(iPr2Im)2(H)(SiHn-1R4-n)] (n = 1, 2) and nickel bis(silyl) complexes cis-[Ni(iPr2Im) 2(SiHn-1R4-n)2] (n = 1, 2, 3) were synthesized by stoichiometric reactions of 1 with hydrosilanes H nSiR4-n, and fully characterized by X-ray diffraction and spectroscopic methods. These hydrido silyl complexes are examples where the full oxidative addition step is hindered. They have, as a result of the remaining Si-H interactions, remarkably short Si-H distances and feature a unique dynamic behavior in solution. Cis-[Ni(iPr2Im)2(H)(SiMePh 2)] (cis-5) shows in solution at room temperature a dynamic site exchange of the NHC ligands, H-D exchange with C6D6 to give the deuteride complex cis-[Ni(iPr2Im)2(D)(SiMePh 2)] (cis-5-D), and at elevated temperatures an irreversible isomerization to trans-[Ni(iPr2Im)2(D)(SiMePh 2)] (trans-5-D). Reactions with sterically less demanding silanes give cis-configured bis(silyl) complexes accompanied by the release of dihydrogen. These complexes display, similarly to the hydrido silyl complexes, interestingly short Si-Si distances. Complex 1 reacts with 4 eq. HSi(OEt) 3, in contrast to all the other silanes used in this study, to give the trans-configured bis(silyl) complex trans-[Ni(iPr2Im) 2Ni(Si(OEt)3)2] (trans-12). The addition of two equivalents of Ph2SiH2 to 1 results, at elevated temperatures, in the formation of the dinuclear complex [{(iPr 2Im)Ni-μ2-(HSiPh2)}2] (6). This diamagnetic, formal Ni(i) complex exhibits a long Ni-Ni bond in the solid state, as established by X-ray diffraction. The capability of the electron rich {Ni(iPr2Im)2} complex fragment to activate Si-H bonds was applied catalytically in the deuteration of Et3Si-H to Et 3Si-D employing C6D6 as a convenient deuterium source. Furthermore, we show that 1 serves as a catalyst for the acceptorless dehydrogenative coupling of Ph2SiH2 to the corresponding disilane Ph2HSi-SiHPh2 and trisilane Ph 2HSi-Si(Ph)2-SiHPh2, and the coupling of PhSiH3 to give a mixture of cyclic and linear polysilanes with high polydispersity (Mw = 1119; Mn = 924; Mw/M n = 1.2). The capability of 1 to catalyze the formal reverse reaction as well is demonstrated by the hydrogenation of disilanes. The hydrogenation of the disilanes Ph2MeSi-SiMePh2 and PhMe 2Si-SiMe2Ph to the corresponding hydrosilanes Ph 2MeSi-H and PhMe2Si-H, respectively, proceeds effectively in the presence of 1 under very mild conditions (room temperature, 1.8 bar H2 pressure).

Reactivity of group 4 benzamidinate complexes towards mono- and bis-substituted silanes and 1,5-hexadiene

Zirconium and titanium bis(benzamidinate) dimethyl complexes were found to be active catalytic precursors for the oligomerization of mono- and bis-substituted silanes. The activation of such complexes, by an excess of MAO or by an equimolar amount of B(C

Electrochemical synthesis of symmetrical difunctional disilanes as precursors for organofunctional silanes

Difunctional disilanes of the general type XR2SiSiR2X (1-5) (X = OMe, H; R = Me, Ph, H) have been synthesized by electrolysis of the appropriate chlorosilanes XR2SiCl in an undivided cell with a constant current supply and in the absence of any complexing agent. Reduction potentials of the chlorosilane starting materials derived from cyclic voltammetry measurements were used to rationalize the results of preparative electrolyses. Organofunctional silanes of the general formula MeO(Me 2)SiC6H4Y (6a-c, 7) were subsequently obtained by the reaction of sym-dimethoxytetramethyldisilane (1) with NaOMe in the presence of p-functional aryl bromides BrC6H4Y (Y = OMe, NEt2, NH2).