Synthesis and Characterization of Monomeric Triarylbismuthine Oxide

Abstract The synthesis and isolation of a bismuth‐based analogue of the venerable triphenylphosphine oxide (Ph 3 PO) has remained a chimera to synthetic chemists for many years, due to its predicted high reactivity and instability. Through the hydrolysis of a cationic fluorotriarylbismuthonium(V) salt, we report here the isolation of unique hydroxytriarylbismuth(V) complexes, which served as precursor for the formation of the elusive monomeric triarylbismuthine oxide Dipp 3 Bi=O. Combined spectroscopic, crystallographic and computational studies provided insight into the bonding situation of the first monomeric triorganobismuth oxide complex. The Dipp 3 Bi=O and Mes 3 BiO⋅LiBAr F complex exhibits O‐atom transfer reactivity, an uncommon reactivity feature for Ar 3 Pn=O.