N‐nacnac stabilized tetrylenes: access to silicon hydride systems via migration processes

Abstract

AbstractThe use of an amino‐functionalized β‐diketiminate (′N‐nacnac′) ligand in low‐valent silicon chemistry is investigated. In particular, the use of (LDipp)SiCl (LDipp=HC{(Me2N)CNDipp}2) to generate silicon‐containing products via metathesis chemistry is explored, in light of previously reported complications arising from heterocycle ring contraction. In the case of Na[C5H5], chloride metathesis is accompanied not by rearrangement of the N‐nacnac ligand, but by a C‐to‐Si hydrogen migration process, generating the hydridosilicon(IV) species (LDipp)Si(H)(C5H4), which features a silafulvene core. The potential intermediate arising from initial chloride/cyclopentadienide substitution can be modelled by the chemistry of the corresponding Ge(II) and Sn(II) systems, which generate (LDipp)E(η1−C5H5) (E=Ge, Sn) via straightforward metathesis chemistry. A Si(II) hydride species can be generated from (LDipp)SiCl via metathesis by making use of a d‐block reagent which can act as both hydride source and coordinative trap for (LDipp)SiH. Thus, the reaction of (LDipp)SiCl with K[(η5−C5H4Me)Mn(CO)2H] leads to the formation of (η5−C5H4Me)Mn(CO)2{Si(H)LDipp} – the first silylene complex containing this half‐sandwich manganese fragment.