13272-89-4Relevant academic research and scientific papers
Gold(I) complexes with chloro(diaryl)silyl ligand. Stoichiometric reactions and catalysis for O-functionalization of organosilane
Kanda, Atsushi,Osakada, Kohtaro,Tsuchido, Yoshitaka
, (2020)
An Au(I) complex with a chloro(diphenyl)silyl ligand [Au(SiPh2Cl)(PCy3)] (1a) is obtained from the reaction of Ph2SiH2 with [AuCl(PCy3)]. (4-FC6H4)2SiH2, (4-MeC6H4)2SiH2, and Ph2GeH2 react with [AuCl(PCy3)] to form complexes with the chlorodiarylsilyl ligand, [Au(SiAr2Cl)(PCy3)] (1b: Ar = C6H4-4-F, 1c: Ar = C6H4-4-Me) and with the chloro(diphenyl)germyl ligand, [Au(GePh2Cl)(PCy3)] (2a), respectively. Complex 1a reacts with H2O to form Ph2SiH(OH) and (Ph2SiH)2O, whereas the reaction of EtOH with 1a yields Ph2SiH(OEt) exclusively. Complex 1a catalyzes the hydrolysis of Ph2SiH2 ([Au]:[H2SiPh2]:[H2O] = 0.05:1.0:10.0) at 60 °C to yield Ph2SiH(OH) and (Ph2SiH)2O. The reaction of Ph2SiH2 with HOEt in the presence of a catalytic amount of 1a affords Ph2SiH(OEt). Both stoichiometric and catalytic reactions using 1a lead to the recovery of [AuCl(PCy3)] from the reaction mixture.
Selective homo- And cross-desilacoupling of aryl and benzyl primary silanes catalyzed by a barium complex
Cheng, Jianhua,Liu, Zhizhou,Shi, Xianghui
, p. 8340 - 8346 (2020/07/07)
Under mild conditions (25 °C, 5 mol% cat.), highly selective homo- and cross-desilacoupling of aryl and benzyl primary silanes to secondary silanes was achieved by the use of the heteroleptic barium aminobenzyl complex [(TpAd,iPr)Ba(CH2C6H4NMe2-o)] (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) (1) as a catalyst. Dihydrosilanes originating from catalytic redistribution and cross-desilacoupling reactions were isolated in fine yields, which demonstrates the feasible application of the barium complex in the syntheses of secondary aryl- and benzylsilanes. This journal is
Divalent Ytterbium Complex-Catalyzed Homo- and Cross-Coupling of Primary Arylsilanes
Liu, Xiaojuan,Xiang, Li,Louyriac, Elisa,Maron, Laurent,Leng, Xuebing,Chen, Yaofeng
supporting information, p. 138 - 142 (2019/01/16)
Redistribution of primary silanes through C-Si and Si-H bond cleavage and reformation provides a straightforward synthesis of secondary silanes, but the poor selectivity and low efficiency severely hinders the application of this synthetic protocol. Here, we show that a newly synthesized divalent ytterbium alkyl complex exhibits unprecedentedly high catalytic activity toward the selective redistribution of primary arylsilanes to secondary arylsilanes. More significantly, this complex also effectively catalyzes the cross-coupling between electron-withdrawing substituted primary arylsilanes and electron-donating substituted primary arylsilanes to secondary arylsilanes containing two different aryls. DFT calculation indicates that the reaction always involve the exothermic formation of a hypervalent silicon upon facile addition of PhSiH3 to the Yb-E (E = C, H) bond. This hypervalent compound can easily either generate directly the Yb-Ph complex, or indirectly through the formation of Yb-H, that is the key complex for the formation of Ph2SiH2.
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.
Dichotomy of Manganese Catalysis via Organometallic or Radical Mechanism: Stereodivergent Hydrosilylation of Alkynes
Yang, Xiaoxu,Wang, Congyang
supporting information, p. 923 - 928 (2018/01/01)
Herein, we disclose the first manganese-catalyzed hydrosilylation of alkynes featuring diverse selectivities. The highly selective formation of E-products was achieved by using mononuclear MnBr(CO)5 with the arsenic ligand, AsPh3. Whereas using the dinuclear catalyst Mn2(CO)10 and LPO (dilauroyl peroxide) enabled the reversed generation of Z-products in good to excellent stereo- and regioselectivity. Such a way of controlling the reaction stereoselectivity is unprecedented. Mechanistic experiments revealed the dichotomy of manganese catalysis via organometallic and radical pathways operating in the E- and Z-selective routes, respectively.
Triangular Triplatinum Complex with Four Bridging Si Ligands: Dynamic Behavior of the Molecule and Catalysis
Tanabe, Makoto,Kamono, Megumi,Tanaka, Kimiya,Osakada, Kohtaro
, p. 1929 - 1935 (2017/06/13)
A triangular triplatinum(0) complex with bridging diphenylsilylene ligands, [{(Pt(PMe3)}3(μ-SiPh2)3] (1a), reacts with H2SiPh2 to produce the 1:1 adduct, [{Pt(PMe3)}3(
Efficient synthesis of substituted diarylsilanes
Gigler, Peter,Herrmann, Wolfgang A.,Kuehn, Fritz E.
experimental part, p. 1431 - 1432 (2010/09/14)
A highly efficient synthesis of substituted diarylsilanes is presented. The treatment of substituted arylbromides with tert-bu-tyllithium in diethyl ether at -78 °C, followed by the addition to dichlorodiethoxysilane at the same temperature, leads to the quantitative formation of diaryldiethoxysilane. Selective substitution of the chlorine atoms allows an aqueous work up in air. Subsequently, the diaryldiethoxysilane is reduced to the corresponding diarylsi-lane by stirring with lithium aluminum hydride in diethyl ether. The product is purified by bulb-to-bulb distillation. This method does not lead to any mono- or tri-substituted products and avoids handling gaseous and explosive dichlorosilane, which is a significant advantage over previously reported procedures. Georg Thieme Verlag Stuttgart.
