38274-75-8Relevant academic research and scientific papers
Electrochemical properties of arylsilanes
Biedermann, Judith,Wilkening, H. Martin R.,Uhlig, Frank,Hanzu, Ilie
, p. 13 - 18 (2019/03/27)
In the past, the electrochemical properties of organosilicon compounds were investigated for both fundamental reasons and synthesis purposes. Little is, however, known about the electrochemical behaviour of hydrogen-bearing arylsilanes. Here, we throw light on the electrochemical properties of 11 arylsilanes compounds, 2 of them synthesized for the first time. The oxidation potentials are found to depend on both the nature and number of the aryl groups. Based on these findings it was possible to establish some variation trends that match the expected structure–property correlations. Furthermore, we present first insights into the electrochemical reaction kinetics behind and identify several soluble electrochemical oxidation products.
Custom Hydrosilane Synthesis Based on Monosilane
Yuan, Weiming,Smirnov, Polina,Oestreich, Martin
supporting information, p. 1443 - 1450 (2018/04/20)
The omnipresence of silicon compounds with carbon substituents in synthetic chemistry hides the fact that, except for certain substitution patterns at the silicon atom, their preparation is often far from trivial. The challenge is rooted in the lack of control over nucleophilic substitution with carbon nucleophiles at silicon atoms with three or four leaving groups. For example, SiCl4 usually converts into intractable mixtures of chlorosilanes, typically requiring several distillation cycles to reach high purity. Accordingly, there is no universal approach to silanes with heteroleptic substitution. Here, using a bench-stable SiH4 surrogate, we introduce a general strategy for the on-demand synthesis of silicon compounds decorated with different aryl and alkyl substituents. Reliable protocols are the basis of the selective and programmable synthesis of dihydro- and monohydrosilanes; aryl-substituted trihydrosilanes are also accessible in a straightforward fashion. These otherwise difficult-to-access hydrosilanes are only three or fewer easy synthetic operations away from the SiH4 surrogate. Synthesizing silicon compounds with different carbon substituents from inorganic silicon precursors, i.e., basic silicon chemicals with hydrogen, halogen, or alkoxy substitution, is an intricate and often insoluble task. It is generally difficult to chemoselectively address one of these groups in chemical reactions, particularly when two or more of those are identical. Complicated separation and purification procedures are the result. The challenge of making these silicon compounds containing silicon–carbon bonds, typically hydro- and chlorosilanes, is accentuated considering their high demand in academia and industry. The present approach is a step forward in solving those limitations. It hinges on the stepwise decoration of the silicon atom of a liquid monosilane surrogate. Further development of this strategy and adjusting it to industrial needs could pave the way to easy access of an even more diverse manifold of silicon compounds for synthetic chemistry and material science. Oestreich and colleagues present an approach to the chemoselective stepwise preparation of hydrosilanes with the general formula R4–nSiHn where n = 1–3 and R can be different aryl and alkyl groups. The starting point is a bench-stable SiH4 surrogate with two Si–H bonds masked as cyclohexa-2,5-dien-1-yl substituents. A sequence of palladium-catalyzed Si–H arylation and B(C6F5)3-promoted deprotection and transfer hydrosilylation enables the programmable synthesis of hydrosilanes, even with three different substituents at the silicon atom.
Carbon-Silicon Bond Formation in the Synthesis of Benzylic Silanes
Visco, Michael D.,Wieting, Joshua M.,Mattson, Anita E.
, p. 2883 - 2885 (2016/07/06)
Sterically encumbered organosilanes can be difficult to synthesize with conventional, strongly basic reagents; the harsh reaction conditions are often low yielding and not suitable for many functional groups. As an alternative to the typical anionic strat
Cooperative hydrogen-bonding effects in silanediol catalysis
Tran, Ngon T.,Wilson, Sean O.,Franz, Annaliese K.
supporting information; experimental part, p. 186 - 189 (2012/03/26)
The importance of cooperative hydrogen-bonding effects and SiOH-acidification is described for silanediol catalysis. NMR binding, X-ray, and computational studies provide support for a unique dimer resulting from silanediol self-recognition. The significa
Pentacoordinate silicon compounds. Reactions of silatranes with nucleophiles
Cerveau, G.,Chuit, C.,Corriu, R. J. P.,Nayyar, N. K.,Reye, C.
, p. 159 - 168 (2007/10/02)
The reactions of hydro, organyl and halosilatranes with nucleophiles have been studied.Substitution involving cleavage of equatorial Si-O bonds is always observed.Silitranes exhibit reactivity quite different from that of analogous trialkoxysilanes or anionic pentacoordinate silicon compounds.
Reactivity of Hypervalent Species: Reactions of Anionic Penta-Coordinated Silicon Complexes towards Nucleophiles
Boudin, Alain,Cerveau, Genevieve,Chuit, Claude,Corriu, Robert J. P.
, p. 101 - 106 (2007/10/02)
The reactivity of anionic penta-coordinated silicon complexes 4-O)2>-Na+ 1 with nucleophilic reagents has been studied. 1 can be reduced to organosilanes RSiH3 by metallic hydrides.Reactions with an excess of Grignard or organolithium reagents (R'MgX or R'Li) gave tetraorganosilanes RSiR'3.When only two molar equivalents of Grignard reagents (R'MgX) or lithium reagents (R'Li) are added to complexs 1 functional silanes RR'2SiX can be prepared.
Process for the preparation of hydrogenosilanes or halogenosilanes
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, (2008/06/13)
A process for the preparation of hydrogenosilanes or halogenosilanes corresponding to the general formula I:
