Year: 2024
Type: article
Abstract: 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.
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
OpenAlex ID: W4405107440