Scholarlink

Abstract <p>Catalytic dehydrocoupling of silanes with alcohols is possible without an additional solvent, and the conversion efficiency depends on the properties of the silane, alcohol, and catalyst. We have shown that in low-polarity solvents, the key intermediates in the reaction of hydrosilanes with fluorinated alcohols (HOR<sup>F</sup>) are tetrel compounds [R<sub>4–<i>n</i></sub>Si(OR<sup>F</sup>)H<sub><i>n</i></sub>]<sup>–</sup>, containing pentacoordinated (hypervalent) silicon, and their dihydrogen-bonded complexes of the type [R<sub>4–<i>n</i></sub>Si(OR<sup>F</sup>)H<sub><i>n</i></sub>]<sup>–</sup>···HOR<sup>F</sup>. However, the dehydrocoupling reaction was not observed when using less acidic, non-fluorinated alcohols as substrates. This work presents the results of a study on the possibility of a solvent-free dehydrocoupling reaction with aliphatic alcohols using the PhSiH<sub>3</sub>–MeOH system as an example in the presence of Et<sub>3</sub>N, as well as palladium and nickel complexes with the pincer ligand (PNP)MX [M = Ni, Pd; X = Cl, H; PNP = bis-(2-diisopropylphosphino-4-methylphenyl)amide], in which the basicity of the amide nitrogen atom approaches the basicity of triethylamine.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Role of the Base in Dehydrocoupling Reaction of Phenylsilane with Methanol

  • 期刊论文

  • 发表日期：

    2026年3月19日

查看全文
  • Vasilisa A. Kulikova,
  • Evgenii I. Gutsul,
  • Oleg A. Filippov,
  • Natalia V. Belkova,
  • Elena S. Shubina

摘要

Abstract

Catalytic dehydrocoupling of silanes with alcohols is possible without an additional solvent, and the conversion efficiency depends on the properties of the silane, alcohol, and catalyst. We have shown that in low-polarity solvents, the key intermediates in the reaction of hydrosilanes with fluorinated alcohols (HORF) are tetrel compounds [R4–nSi(ORF)Hn]–, containing pentacoordinated (hypervalent) silicon, and their dihydrogen-bonded complexes of the type [R4–nSi(ORF)Hn]–···HORF. However, the dehydrocoupling reaction was not observed when using less acidic, non-fluorinated alcohols as substrates. This work presents the results of a study on the possibility of a solvent-free dehydrocoupling reaction with aliphatic alcohols using the PhSiH3–MeOH system as an example in the presence of Et3N, as well as palladium and nickel complexes with the pincer ligand (PNP)MX [M = Ni, Pd; X = Cl, H; PNP = bis-(2-diisopropylphosphino-4-methylphenyl)amide], in which the basicity of the amide nitrogen atom approaches the basicity of triethylamine.