A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities.
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Reactions of trans-[Fe(CO)2(NO)(As((CH2)n)3As)]+ BF4- (n = 10, 12, 14) and Bu4N+ Cl- afford the title compounds As((CH2)n)3As, which upon reaction (n = 14) with MCl2 (M = Pt, Ni), Rh(CO)(Cl), and Fe(CO)3 sources reconstitute cage like complexes trans-MLn(As((CH2)14)3As). Reactions with H2O2 and BH3 give the corresponding arsine oxides and boranes. Crystal structures of metal-free species reveal out,out isomers, but cage complex formation is proposed to entail homeomorphic isomerization to in,in isomers with endo directed lone pairs.