Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes

Danila Gasperini, Andrew King, Nathan Coles, Mary Mahon, Ruth Webster

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

A detailed synthetic investigation into the dehydrocoupling of silanes with amines, phosphines, and alcohols using an iron precatalyst (1) is presented. We have furnished over 30 examples of aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N-H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed in depth. Beyond this we have explored the substrate scope of phosphinosilane formation which shows a preferential heterodehydrocoupling to give the phosphinosilane with primary and secondary silanes. Silylethers can also be prepared and alcohols that contain alkene functionality do not show any tendency to reduce the double bond.

Original languageEnglish
Pages (from-to)6102-6112
Number of pages11
JournalACS Catalysis
Volume10
Issue number11
Early online date6 May 2020
DOIs
Publication statusPublished - 5 Jun 2020

Keywords

  • dehydrocoupling
  • homogeneous catalysis
  • iron
  • reaction mechanisms
  • silanes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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