An Isolable Base-Stabilized Diazosilenyl Cation

In contrast to the emerging chemistry of stable diazoalkenes, there are not yet any studies devoted to heavier silicon analogues, diazosilenes. Here, we report the synthesis of a base-stabilized diazosilenyl cation 2 by the reaction of base-stabilized C-phosphonio-silyne 1 with N₂O. This silicon analog of diazoalkenes 2 exhibits a remarkable stability thanks to the coordination of phosphine and phosphine oxide ligands at the cationic silicon center. In addition, DFT calculations predict that, due to a particular stabilizing effect of the electropositive silicon atom, for diazosilenes (R₂Si=C=N₂), the presence of π-donor substituents is not essential to prevent N₂ dissociation, contrary to carbon analogues. Interestingly, diazosilenyl cation 2 tends to isomerize into (silylene)(phosphonio)diazomethane 7 via a 1,2-phosphine ligand migration and thus exhibits dual reactivity as a diazoalkene and as a diazo-substituted silylene.