ChemInform Abstract: The Reducing System Trialkylsilane ‐ Transition Metal Acetylacetonate. Part 1. Reduction of Aliphatic Monocarboxylic Halogenides with Trialkylsilanes in the Presence of Nickel Acetylacetonate.

Abstract

The carboxylic halides (I) react with the trialkylsilanes (II) in the presence of 1 ‐ 3 mole percent nickel acetylacetonate to give the esters (III) and the trialkylhalosilanes (IV).

Iron-Catalyzed Chlorination of Silanes

“…A radical-induced substitution of silanes in tetrachloromethane has likewise been described, providing good yields of the corresponding chlorosilanes . Voronkov and co-workers have reported the formation of chlorosilanes as side products in the ferric acetylacetonate catalyzed reduction of carboxylic acid chlorides to alcohols . Halogenated silanes have also been prepared using Ni(II) chloride and Pd(II) chloride catalysts in combination with suitable halogen-containing reagents or solvents, including tetrachloromethane .…”

Kinetic and Theoretical Investigation of Iron(III)‐Catalyzed Silane Chlorination

“…The present revision of the reaction mechanism is based on the oxophilicity of iron(III), and thus its potential functioning as Lewis acid via coordination to oxygen in acetyl chloride. Inspired by the previous investigation by Voronkov and co‐workers on iron(III) acetylacetonate catalyzed reductive formation of esters and aldehydes from acyl chlorides, in which silyl chloride byproduct formation from the triethylsilane reducing agent used was observed, a general reaction pathway for the revised mechanism was sketched. First, coordination of FeCl 3 to the acetyl chloride ( 1 in Scheme ), followed by reduction of the acid chloride to aldehyde ( 2 in Scheme ), takes place.…”