Facile Access to Dative, Single, and Double Silicon−Metal Bonds Through M−Cl Insertion Reactions of Base‐Stabilized Si^II Cations

Abstract

Silicon(II) cationsc an offer fascinating reactivity patterns due to their unique electronic structure:alone pair of electrons,t wo empty po rbitals and ap ositive charge combined on as ingle silicon center.W en ow reportt he facile insertion of N-heterocyclicc arbene( NHC)-stabilized silyliumylidene ions into MÀCl bonds (M = Ru, Rh), forming a series of novel chlorosilylene transition-metal complexes. Theoretical investigations revealed ar eactionm echanism in which the insertioni nto the MÀCl bond with concomitant 1,2-migration of as ilicon-bound NHC to the transition metal takes place after formation of an initial silyliumylidene transition-metal complex.T he mechanism could be verified experimentally through characterization of the intermediate complexes. Furthermore, the obtained chlorosilylene complexes can be conveniently utilized as synthons to access SiÀMa nd Si=Mb onding motifs bondst hrough reductive dehalogenation.[a] P. Frisch, Prof. Dr.S.I noue Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme5.Reductiono f6a and 7a with KC 8 to silyl complexes 8 and 9 and to silylenecomplex 10.

Tetryliumylidene ions in synthesis and catalysis

“… 86 Additionally, 9 can undergo a facile insertion into M–Cl bonds (M = Ru, Rh), forming the chlorosilylene transition-metal complexes 32 ( Scheme 5 ). 87 …”

“…86 Additionally, 9 can undergo a facile insertion into M-Cl bonds (M = Ru, Rh), forming the chlorosilylene transition-metal complexes 32 (Scheme 5). 87 When reacted with elemental sulphur, the bis(iminophosphorane) coordinated chloro-silyliumylidene 14 is oxidised to the chlorosilathionium salt 33 (Scheme 6). 81 This reactivity is similar to the reactivity of 9 with chalcogens.…”