Synthesis and Reactivity of Base-Stabilized and Base-Free Silaimidoyl Bromides

Pauline Hädinger; Maximilian P Müller; Alexander Hinz

doi:10.1021/acs.inorgchem.3c03711

Synthesis and Reactivity of Base-Stabilized and Base-Free Silaimidoyl Bromides

Inorg Chem. 2024 Jan 29;63(4):1997-2004. doi: 10.1021/acs.inorgchem.3c03711. Epub 2024 Jan 11.

Authors

Pauline Hädinger¹, Maximilian P Müller¹, Alexander Hinz¹

Affiliation

¹ Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Gebäude 30.45, 76131 Karlsruhe, Germany.

PMID: 38207101
DOI: 10.1021/acs.inorgchem.3c03711

Abstract

The reactivity of the base-free bromosilylene ^dtbpCbzSiBr (^dtbpCbz = 1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl) toward carbodiimides and azides was studied in order to generate base-stabilized and base-free silaimidoyl bromides, respectively. The steric bulk of carbodiimides and azides allows control over the reactivity. While with small substituents such as tert-butyl or adamantyl, the reactions cannot be stopped at the Si═N stage, with large substituents, they lead to C-H activation in the product. The Dipp substituent (Dipp = 2,6-diisopropylphenyl) allowed the isolation of the silaimidoyl bromide ^dtbpCbzSi(Br)NDipp and its CNDipp-coordinated analogue. The reactivity of the Si═N double bond species was studied with respect to cycloaddition and donor exchange reactions.