Facile access to cationic methylstannylenes and silylenes stabilized by E‒Pt bonding and their methyl group transfer reactivity

We 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 neutral N-donor ligand bind-ing 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 syn-thesis of MeSnII:+ derivatives.