Oxidation reactions of a versatile, two-coordinate, acyclic iminosiloxysilylene

Abstract

A comprehensive reactivity study of an acyclic iminosiloxysilylene provides further insights into this relatively unexplored compound class and revealed analogies to both classical transition metal complexes and the lighter silicon congener carbon.

Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

“…This observation is in agreement with a previously computed σ‐bond metathesis H 2 activation pathway mediated by silylene . Recently, our group reported the reactivity of the imino(siloxy)silylene 21 . The reaction of silylene 21 with 1 equivalent of NH 3 affords the hydroamination product 51 .…”

“…In this reaction, the cleavage of two P–P bonds of P 4 and the regioselective formation of four new Si–P bonds were observed. In addition, imino(siloxy)silylene 21 was found to occur via the oxidative addition of 1 equivalent of P 4 to give (IPrN)( t Bu 3 SiO)Si(P 4 ) ( 64 ), which is different from that observed for the vinyl(silyl)silylene 27 …”

Where silylene–silicon centres matter in the activation of small molecules

“…The acyclic two-coordinate N,O-silylene 117 also cleaves N-H bond of ammonia, affording aminosilane 118 as described by Inoue very recently (Scheme 45). 84 The novel tetrasilyldisilene displaying bis(silyl)silylene reactivity also shows high reactivity towards NH 3 . The hydroamination is achieved by treating an n-hexane solution of 11/11 0 with one molar equivalent of NH 3 along with an apparent colour change from blood red to pale yellow and the formation of 119.…”

Reversible Activation and Transfer of White Phosphorus by Silyl‐Stannylene

“…Recently, low valent heavier group 14 carbene homologues, namely tetrylenes ([R 2 E:] E=Si, Ge), which are in the +II oxidation state, have given new impetus to the field of P 4 activation [4] . Examples of both silylenes [4a,c,d,f, 5] and germylenes have been reported to activate P 4 [4b] . Notably, a diaryl germylene [ Mes Ter 2 Ge:], ( Mes Ter=2,6‐(2,4,6‐Me 3 C 6 H 2 ) 2 C 6 H 3 ] provided the first main group mediated reversible activation of the P−P bond in P 4 [4b] .…”