The First Monomeric β‐Diketiminate Stabilized Four‐Coordinated Bismuth(III) Bistrifluoromethanesulfonate

Abstract

The sterically encumbered β-diketiminate bismuth(III) bistriflate, LBi(OSO 2 CF 3 ) 2 [L = HC{(CMe)N(2,6-iPr 2 C 6 H 3 )} 2 ] (2) was prepared from a facile one-pot reaction between potassium β-diketiminate LK (1) and bismuth(III) triflate. It was characterized by elemental analysis, FT-IR, 617 molecular structure of 2 was further confirmed by single-crystal X-ray crystallography. The solid-state structure of 2 reveals a first structurally characterized monomeric β-diketiminate supported group 15 bistriflate. The coordination number of bismuth is four. Figure 1. Known β-diketiminate supported triflate derivatives of group 15 molecules.

Neutral and Cationic β-Ketoiminato Bismuth Complexes

“…Obtaining low coordinate bismuth compounds and generation of cationic bismuth species to exploit their Lewis acidity are the major focus in this area . A variety of anionic nitrogen donor bidentate ligands including amidinates, N ‐functionalized amides, pyrrole based N,N chelators, and β‐diketiminates have been explored in bismuth coordination chemistry. In 2011, Zhu and co‐workers investigated the synthetic access to [(β‐diketiminato)BiCl 2 ] type of complexes.…”

“…In 2011, Zhu and co‐workers investigated the synthetic access to [(β‐diketiminato)BiCl 2 ] type of complexes. [6b] The expected dimeric [(β‐dikeminato)BiCl(μ‐Cl)] 2 (Figure ) was isolated at temperatures below –15 °C. A is thermally unstable at ambient conditions and transforms to B , which is a result of intramolecular C–H bond activation.…”

“…Because of its instability, the reactivity of [(β‐diketiminato)BiCl 2 ] is not well explored. However, [(β‐diketiminato)BiI(μ‐I)] 2 [6c] and the monomeric [(β‐diketiminato)Bi(OOCCF 3 ) 2 ][6b] and [(β‐diketiminato)Bi(OTf) 2 ][6a] have been successfully prepared and are thermally stable. Yet, no progress has been made in this chemistry, towards accessing cationic bismuth species.…”