Premium
Synthesis of a Metallo‐Iminosilane via a Silanone–Metal π‐Complex
Author(s) -
Hadlington Terrance J.,
Szilvási Tibor,
Driess Matthias
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201708923
Subject(s) - carbene , boranes , reactivity (psychology) , hydroboration , chemistry , medicinal chemistry , metal , stereochemistry , boron , catalysis , organic chemistry , medicine , alternative medicine , pathology
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.