Synthesis of a Metallo‐Iminosilane via a Silanone–Metal π‐Complex

Facile oxygenation of the acyclic amido‐chlorosilylene bis(N‐heterocyclic carbene) Ni 0 complex [{N(Dipp)(SiMe 3 )ClSi:→Ni(NHC) 2 ] ( 1 ; Dipp=2,6‐ i Pr 2 C 6 H 4 ; N‐heterocyclic carbene=C[( i Pr)NC(Me)] 2 ) with N 2 O furnishes the first Si‐metalated iminosilane, [DippN=Si(OSiMe 3 )Ni(Cl)(NHC) 2 ] ( 3 ), in a rearrangement cascade. Markedly, the formation of 3 proceeds via the silanone (Si=O)–Ni π‐complex 2 as the initial product, which was predicted by DFT calculations and observed spectroscopically. The Si=O and Si=N moieties in 2 and 3 , respectively, show remarkable hydroboration reactivity towards H−B bonds of boranes, in the former case corroborating the proposed formation of a (Si=O)–Ni π‐complex at low temperature.