Phosphaarsenes – Combining Phospha‐ and Arsa‐Wittig‐Reagents

Dipnictenes of the type RPn=PnR (Pn = P, As, Sb, Bi) can be viewed as dimers of the corresponding pnictinidenes R−Pn. Phosphanylidene- and arsanylidenephosphoranes (R−Pn(PMe3); Pn = P, As) have been shown to be versatile synthetic surrogates for the delivery of pnictinidene fragments. We now report that thermal treatment of 1:1 mixtures of R−P(PMe3) and R’−As(PMe3) gives access to arsaphosphenes of the type RP=AsR’. Three examples are presented and the properties and reactivity of Mes*P=AsDipTer (1) (Mes* = 2,4,6-tBu3-C6H2; DipTer = 2,6-(2,6-iPr2C6H3)2-C6H3) were studied in detail. Solid state 31P NMR spectroscopy revealed a large 31P NMR chemical shift anisotropy with a span of ca. 920 ppm for 1 while computational methods were employed to investigate this pronounced magnetic deshielding of the P atom in 1. In the presence of the carbene IMe4 (IMe4 = :C(MeNCMe)2) 1 is shown to be split into the corresponding NHC adducts Mes*P(IMe4) and DipTerAs(IMe4), which is additionally shown for diarsenes.