Anionische 1,2-(O→N)- und neutrale 1,2-(N→O, O→N)-Silylgruppen-Wanderung — Synthese isomerer Tris(silyl)hydroxylamine und eines Silylaminodisiloxans

Add time:07/11/2019    Source:sciencedirect.com

The lithium derivative of N,O-bis(tert-butyldimethylsilyl)hydroxylamine, Me3CSiMe2NHOSiMe2CMe3 (1), is isolated as the first dimeric O-lithium-N,N-bis(silyl)hydroxylamide, [(THF)LiON(SiMe2CMe3)2]2 (2). The tendency of the hard Lewis-acid lithium to bind the hard Lewis-base oxygen explains the O→N-silyl group migration. 2 reacts with tert-butyltrifluorosilane to give the tris(silyl)hydroxylamine Me3CSiF2ON(SiMe2CMe3)2 (3). An irreversible rearrangement involving positional exchange between the fluorosilicon group on oxygen and one organosilicon group on nitrogen in 3 leads to the formation of the isomeric tris(silyl)hydroxylamine Me3CSiMe2ON(SiMe2CMe3)SiF2CMe3 (4). The rearrangement proceeds via a dyotropic transition state. 4 undergoes an intramolecular thermal rearrangement involving the insertion of a silyl moiety into the NO bond and the transfer of a methyl group from silicon to nitrogen. The silylaminodisiloxane Me3CSiMe2OSiMe(CMe3)NMeSiF2CMe3 (5) is obtained. The influence of the effects of the substituents of the product formation is discussed and the crystal structure of 2 is reported.

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