16165-87-0Relevant articles and documents
Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
supporting information, p. 8988 - 8994 (2021/11/23)
A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
Spectroscopic investigation of the reactivity of Cp*Ru(PiPr2Ph)X toward H2 and silanes: Formation in solution of Cp*Ru(PiPr2Ph)(H)3 and Cp*Ru(PiPr2Ph)(H)2Y (Y = Halide, OR, and SiR′3)
Johnson, Todd J.,Coan, Paul S.,Caulton, Kenneth G.
, p. 4594 - 4599 (2008/10/08)
Reaction of Cp*RuLX (L = PiPr2Ph; X = Br, I, OSiPh3, NHPh, and OCH2CF3, called ORf) with H2 gives, at -60 °C, Cp*RuLX(H)2, where the two hydride ligands are assigned cisoid positions using 1H NMR spectra. These molecules (except X = Br and I) react with additional H2 to give Cp*RuL(H)3 and liberate HX. Mechanistic possibilities are discussed. Reaction of Cp*RuL(ORf) with HSiR3 (R = Me, Ph, OMe) gives Cp*RuL(H)2SiR3 and (RfO)SiR3. Reaction of Cp*RuL(ORf) with H2SiPh2 gives the two products Cp*RuL(H)2(SiXPh2) (X = H and ORf). Reversible equilibria make these species unstable toward isolation. Mechanistic studies are consistent with the presence of a common intermediate, for which H2SiPh2 and HSi(ORf)Ph2 compete.
