Atropo-enantioselective C-H functionalization reactions are largely limited to the dynamic kinetic resolution of biaryl substrates through the introduction of steric bulk proximal to the axis of chirality. Reported herein is a highly atropo-enantioselective palladium(0)-catalyzed methodology that forges the axis of chirality during the C-H functionalization process, enabling the synthesis of axially chiral dibenzazepinones. Computational investigations support experimentally determined racemization barriers, while also indicating C-H functionalization proceeds by an enantio-determining CMD to yield configurationally stable eight-membered palladacycles.

A family of novel dimetallic Bi(iii) and Bi(v) complexes is reported. Structural analysis of the complexes in the solid state permitted the study of the Bi–Bi distance and its impact in the catalytic redox properties.

A series of cationic fluorotriarylbismuthonium salts bearing differently substituted aryl groups (Ar = 9,9-Me 2 -9H-xanthene, Ph, Mes, and 3,5- t Bu-C 6 H 3 ) have been synthesized and characterized. While the presence of simple phenyl substituents around the Bi center results in a polymeric structure with three Bi centers in the repeating monomer, substituents at the ortho - and meta -positions lead to cationic mono- and dinuclear fluorobismuthonium complexes, respectively. Preparation of all compounds is accomplished by fluoride abstraction from the parent triaryl Bi(V) difluorides using NaBAr F (BAr F – = B[C 6 H 3 -3,5-(CF 3 ) 2 ] 4 – ). Structural parameters were obtained via single crystal X-ray diffraction (XRD), and their behavior in solution was studied by NMR spectroscopy. Trinuclear and binuclear complexes are held together through one bridging fluoride (μ-F) between two Bi(V) centers. In contrast, the presence of Me groups in both ortho -positions of the aryl ring provides the adequate steric encumbrance to isolate a unique mononuclear nonstabilized fluorotriarylbismuthonium cation. This compound features a distorted tetrahedral geometry and is remarkably stable at room temperature both in solution (toluene, benzene and THF) and in the solid state.

Atropo-enantioselective C À Hf unctionalization reactions are largely limited to the dynamic kinetic resolution of biaryl substrates through the introduction of steric bulk proximalt ot he axis of chirality.R eported herein is ah ighly atropo-enantioselective palladium(0)-catalyzed methodology that forges the axis of chirality during the C À Hf unctionalization process,e nabling the synthesis of axially chiral dibenzazepinones.C omputational investigations support experimentally determined racemization barriers,w hile also indicating CÀHf unctionalization proceeds by an enantio-determining CMD to yield configurationally stable eight-membered palladacycles.