A Multidimensional Approach to Carbodiphosphorane–Bismuth Coordination Chemistry: Cationization, Redox-Flexibility, and Stabilization of a Crystalline Bismuth Hydridoborate

Bismuth complexes stabilized by carbon-based donor ligands are underserved by their instability, often due to facile ligand dissociation and deleterious protonolysis. Herein, we show that the ortho -bismuthination of hexaphenylcarbodiphosphorane enables a robust framework with geometrically constrained carbone–bismuth bonding interactions, which are highly tunable by cationization. The carbodiphosphorane bismuth halides ( 1 and 2 ) are remarkably air-stable and feature unprecedented trans carbone C–Bi–X ligation, resulting in highly elongated Bi–X bonds. In contrast to known carbone–bismuth complexes, hydrolytic activation of the carbone yields well-defined organobismuth complexes, and subsequent dehydrohalogenation is feasible using potassium bis(trimethylsilyl)amide or N-heterocyclic carbenes. The redox-flexibility of this framework was evaluated in the high catalytic activity of 1 and 2 for silylation of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) under mild conditions (50 °C, 24–96 h) and low catalyst loadings (5–10 mol %), which suggests the accessibility of short-lived hydridic and radical bismuth species. The reaction of 1, PhSiH 3, and tris(pentafluorophenyl)borane (BCF) yields the first crystallographically characterized bismuth hydridoborate complex as an ionic species ( 9 ), presumably by BCF-mediated hydride abstraction from an unobserved [Bi]–H intermediate. All isolated compounds have been characterized by heteronuclear NMR spectroscopy and X-ray crystallography, and the bonding situation in representative complexes ( 1, 2, 5, and 9 ) were further evaluated using density functional theory.