3 years ago

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

Synthesis of a Metallo-Iminosilane via a Silanone–Metal π-Complex
Matthias Driess, Terrance J. Hadlington, Tibor Szilvási
Facile oxygenation of the acyclic amido-chlorosilylene bis(N-heterocyclic carbene) Ni0 complex [{N(Dipp)(SiMe3)ClSi:Ni(NHC)2] (1; Dipp=2,6-iPr2C6H4; N-heterocyclic carbene=C[(iPr)NC(Me)]2) with N2O furnishes the first Si-metalated iminosilane, [DippN=Si(OSiMe3)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. A piece of π: An acyclic silylene–Ni0 complex undergoes facile oxidation with N2O to give silanone–Ni0 π-complex 1 at low temperature. Upon warming, a cascade rearrangement takes place that exclusively yields the Si-metalated iminosilane 3. Remarkably, the Si=O and Si=N bonds in these complexes readily undergo addition reactions with hydroboranes even though such processes typically require a catalyst for the C=O and C=N analogues.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201708923

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