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.
author list (cited authors)
Zarcone, S. R., Verardi, P. J., Bhuvanesh, N., & Gladysz, J. A.
complete list of authors
Zarcone, Samuel R||Verardi, Peter J||Bhuvanesh, Nattamai||Gladysz, John A