Structure and Rearrangement Reactions of Bis(organosilyl)(organostannyl)hydroxylamines: A Joint Theoretical/Experimental Study

Abstract

O-Lithium-N,N-bis(tert-butyldimethylsilyl)hydroxylamide reacts with chlorotrimethylstannane to give N,O-bis(tert-butyldimethylsilyl)-N-(trimethylstannyl)hydroxylamine (1), the crystal structure of which is presented. The primarily formed N,N-bis(tert-butyldimethylsilyl)-O-(trimethylstannyl)hydroxylamine undergoes a dyotropic rearrangement. This reaction mechanism is corroborated by quantum-chemical calculations (B3LYP), partly employing an effective core potential for tin. The possibility for insertion of a stannyl group has been studied by quantum-chemical calculations. The transition states in the various rearrangement reactions of the bis(organylsilyl)stannylhydroxylamine system are discussed in detail.