A surprise landing on the of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities.

Reactions of -[Fe(CO)(NO)(As((CH))As)] BF ( = 10, 12, 14) and BuN Cl afford the title compounds As((CH))As, which upon reaction ( = 14) with MCl (M = Pt, Ni), Rh(CO)(Cl), and Fe(CO) sources reconstitute cage like complexes -ML(As((CH))As). Reactions with HO and BH give the corresponding arsine oxides and boranes. Crystal structures of metal-free species reveal , isomers, but cage complex formation is proposed to entail homeomorphic isomerization to , isomers with directed lone pairs.