789-25-3Relevant articles and documents
Biernbaum,Mosher
, p. 6221 (1971)
The Role of (tBuPOCOP)Ir(I) and Iridium(III) Pincer Complexes in the Catalytic Hydrogenolysis of Silyl Triflates into Hydrosilanes
Berthet, Jean-Claude,Cantat, Thibault,Durin, Gabriel,Nicolas, Emmanuel,Thuéry, Pierre
supporting information, (2021/12/09)
Hydrosilanes are convenient reductants for a large variety of organic substrates, but they are produced via energy-intensive processes. These limitations call for the development of general catalytic processes able to transform Si-O into Si-H bonds. We report here the catalytic hydrogenolysis of R3SiOTf (R = Me, Et, and Ph) species in the presence of a base (e.g., NEt3), by the hydride complexes [(tBuPOCOP)IrH(X)] (X = H and OTf; (tBuPOCOP = [C6H3-2,6(OPtBu)2]. Syntheses and crystal structures of new iridium(I) and iridium(III) complexes are presented as well as their role in the R3SiOTf to R3SiH transformation. The mechanisms of these reactions have been examined by DFT studies, revealing that the active species involved in the reduction of the Si-OTf vs Si-Cl bond are different. The rate-determining transition state is a base-assisted splitting of H2, forming an iridium(III) dihydride species.
Continuous-flow Si-H functionalizations of hydrosilanesviasequential organolithium reactions catalyzed by potassiumtert-butoxide
Lee, Hyune-Jea,Kwak, Changmo,Kim, Dong-Pyo,Kim, Heejin
supporting information, p. 1193 - 1199 (2021/02/26)
We herein report an atom-economic flow approach to the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanesviaserial organolithium reactions catalyzed by earth-abundant metal compounds. Based on the screening of various additives, we found that catalytic potassiumtert-butoxide (t-BuOK) facilitates the rapid reaction of organolithiums with hydrosilanes. Using a flow microreactor system, various organolithiums bearing functional groups were efficiently generatedin situunder mild conditions and consecutively reacted with hydrosilanes in the presence oft-BuOK within 1 min. We also successfully conducted the di-funtionalizations of dihydrosilane by sequential organolithium reactions, extending to a gram-scale-synthesis. Finally, the combinatorial functionalizations of trihydrosilane were achieved to give every conceivable combination of tetrasubstituted organosilane libraries based on a precise reaction control using an integrated one-flow system.
Highly selective redistribution of primary arylsilanes to secondary arylsilanes catalyzed by Ln(CH2C6H4NMe2-: O)3@SBA-15
Guo, Chenjun,Li, Min,Chen, Jue,Luo, Yunjie
supporting information, p. 117 - 120 (2019/12/25)
Rare-earth metal tris(aminobenzyl) complexes Ln(CH2C6H4NMe2-o)3 (Ln = La, Y) were grafted onto the dehydroxylated periodic mesoporous silica support SBA-15 to generate the organometallic-inorganic hybrid materials Ln(CH2C6H4NMe2-o)3@SBA-15 (Ln = La (2a), Y (2b)), which demonstrated extremely high selectivity (>99%) in catalyzing the redistribution of primary arylsilanes to secondary arylsilanes without the requisition of strict control of the reaction conditions. The hybrid materials still showed a perfect selectivity and activity after three catalytic cycles.