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

Akachukwu D. Obi, Diane A. Dickie, William Tiznado, Gernot Frenking, Sudip Pan, Robert J. Gilliard

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

Resumen

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 carboneC-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, PhSiH3, 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.

Idioma originalInglés
Páginas (desde-hasta)19452-19462
Número de páginas11
PublicaciónInorganic Chemistry
Volumen61
N.º48
DOI
EstadoPublicada - 5 dic. 2022

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Química inorgánica

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