A Redox‐Confused Bismuth(I/III) Triamide with a T‐Shaped Planar Ground State

Abstract

Abstract Reaction of a tethered triamine ligand with Bi(NMe 2 ) 3 gives a Bi triamide, for which a Bi I electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi−N and P−N bond polarities. Although considerable Bi I character is indicated for the title Bi triamide, it exhibits reactivity similar to Bi III electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N ‐oxide or W(CO) 5 . The product of the former shows evidence of coordination‐induced oxidation state change at bismuth.