Facile Access to Cationic Methylstannylenes and Silylenes Stabilized by E−Pt Bonding and their Methyl Group Transfer Reactivity**

Abstract

AbstractWe describe a family of cationic methylstannylene and chloro‐ and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn:+ are stabilized by coordination to PtII and are formed by facile Me group transfer from dimethyl or monomethyl PtII complexes, in the latter case triggered by concomitant B−H, Si−H, and H2 bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl− removal from HSiCl3 under ambient conditions. The computational studies show that stabilization of cationic methylstannylenes and cationic silylenes is achieved through weak coordination to a neutral N‐donor ligand binding pocket. The analysis of the electronic potentials, as well as the Laplacian of electron density, also reveals the differences in the character of Pt−Si vs. Pt−Sn bonding. We demonstrate the importance of a ligand‐supported binuclear Pt/tetrel core and weak coordination to facilitate access to tetrylium‐ylidene Pt complexes, and a transmetalation approach to the synthesis of MeSnII:+ derivatives.