Carsten Knapp

Alkylation of OPF3 by MeOSO+AsF−6: the unexpected formation of a dioxadiarsetane☆

Abstract Attempts to alkylate OPF3 with CH3OSO+AsF−6 unexpectedly led to the formation of (CH3OAsF4)2 (1) a four-membered A2O2 heterocycle. 1 decomposes slowly to give (CH3)3O+AsF−6 (2) and {(OAsF3)n}. The adduct F5Sb·OPF3 (4) was isolated from OPF3 and CH3OSO+SbF−6. OPF2NMe2 and CH3OSO+AsF−6 also yielded the corresponding adduct F2(Me2N)PO·AsF5 (5). Reaction mechanisms are discussed, the structures of 1, 2 and 4 are reported.

F3CCN5S3, A BICYCLIC MULTIFUNCTIONAL SULFUR-NITROGEN LIGAND

The bicyclic sulfur-nitrogen heterocycle F3CCN5S3 (1) was investigated as a donor and acceptor toward H+, metal cations, and F−. Whereas the protonated species F3CCN5S3H+ AsF6 − (2) can be isolated, the product of the reaction with F− is unstable and decomposes among other products to TAS+ F3CCN5S3NC(NH2)CF3 − (3), which is isolated from this reaction in small amounts.