Atom Swapping on Aromatic Rings: Conversion from Phosphinine Pincer Metal Complexes to Metallabenzenes Triggered by O<sub>2</sub> Oxidation
Koichiro Masada, Shuhei Kusumoto, Kyoko Nozaki
Abstract
Abstract Herein, we report a novel method for the synthesis of metallabenzenes by swapping the phosphorus atom in an aromatic phosphinine ring with transition metal fragments. The oxidation of a phosphine‐phosphinine‐phosphine pincer iridium complex by O 2 triggered the replacement of the phosphorus atom of the phosphinine ring by an iridium fragment to afford iridabenzene. Dianionic rhodabenzene was also synthesized from a phosphinine rhodium complex by oxidation of the phosphorus atom, followed by subsequent reduction using metallic potassium. The aromaticity of the newly synthesized irida‐ and rhoda‐benzenes was evaluated both experimentally and theoretically.
Topics & Concepts
Pincer movementPhosphineIridiumRing (chemistry)RhodiumChemistryAromaticityTransition metalMetalAtom (system on chip)PhosphorusMedicinal chemistryPhotochemistryCatalysisOrganic chemistryMoleculeEmbedded systemComputer scienceSynthesis and characterization of novel inorganic/organometallic compoundsOrganoboron and organosilicon chemistryCoordination Chemistry and Organometallics