ChemInform Abstract: Homolytic Reactions of Ligated Boranes. Part 14. ESR Studies of Ring Opening of Cycloalkylaminyl‐Borane Radicals and Reactions of Aminyl‐Borane Radicals with Silicon‐Containing Compounds.

Abstract

095ChemInform Abstract Aminyl-borane radicals (II) are generated photochemically from amine-boranes such as (I) either in cyclopropane/oxirane or in tBuOH/tert.-pentyl alcohol. The relative rates of β-hydrogen-atom transfer from (IIa) to Me2C=CMe2 and furan indicate this reaction to be bimolecular and it does not involve prior β-scission of (IIa) to give a free hydrogen atom. H-atom-transfer from (II) to some silanes such as Me3Si-CH2-CH=CH2, Me3Si-CH2-CMe=CH2, and Me3Si-SiMe3 is studied as well. The cycloalkylaminyl-borane radicals (IIb) undergo rapid ring opening to give the alkyl radicals (III) while (IIc) do not.