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

本项目的目标是分离潜在的二自由基(类)双曼烯的稳定的衍生物和相关的混合烟原BiPn衍生物(Pn=P，As，Sb)。该项目的里程碑之一将是对其(电子)结构的研究：由于铋的原子轨道较大且弥散，双芳族体系和开壳双自由基形式似乎是合理的，其较大的原子半径也可能允许跨环的BiBi键，从而产生双环结构基元。对闭壳结构的单态-三态能隙进行了研究。碳骨架上大体积取代基引起的空间位阻将抑制沿铋原子的分子间二聚反应。我们将研究目标化合物与氢、一氧化碳、二氧化碳、烯烃和炔烃等小分子的反应活性，旨在建立和合理双核二氮杂多氧自由基(OID)S的类过渡金属行为。这些目标化合物将被测试为通过自由基途径形成脱氢E-E键的新型催化剂。

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.