Synthesis, Characterization and Reactivity of Diradicaloid 9,10-Bismanthrene Derivatives and Related Mixed Bi/Pn (Pn = P, As, or Sb) Species

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The isolation of a stable derivative of the potentially diradical(oid) bismanthrene and related mixed-pnictogen Bi/Pn derivatives (Pn = P, As, Sb) is the aim of this project. One of the milestones of this project will be the investigation of their (electronic) structure: because of the large and diffuse atomic orbitals of Bi, a bismaaromatic system as well as an open-shell diradicaloid form appear reasonable, and its large atomic radius might also allow transannular Bi–Bi bonding, resulting in a bicyclic structural motif. Singlet-triplet energy gaps of the closed-shell structures will be studied. Steric hindrance induced by bulky substituents at the carbon framework will supress intermolecular dimerization along the Bi atoms. The reactivity of the target compounds towards small molecules such as hydrogen, carbon monoxide, carbon dioxide, alkenes, and alkynes will be investigated, aiming to establish and rationalise transition-metal-like behaviour in (mixed) dinuclear pnictogen diradical(oid)s. The compounds targeted herein will be tested as new types of catalysts for dehydrogenative E–E bond formation (E = N, P) via radical pathways.