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

双自由基 9,10-铋衍生物和相关混合 Bi/Pn（Pn = P、As 或 Sb）物质的合成、表征和反应性

• 批准号: 465414604
• 负责人: Dr. Dennis Rottschäfer
• 金额: --
• 依托单位: Arbeitsgruppe Lichtenberg
• 依托单位国家: 德国
• 项目类别: WBP Position
• 财政年份: 2021
• 资助国家: 德国
• 起止时间: 2020-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/465414604?language=en
• 关键词: Synthesis; Characterization; Reactivity; Diradicaloid; 10

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.

该项目的目的是分离潜在的脏（OID）bismanththene和相关的混合PNICTOGON BI/PN衍生物（Pn = P，AS，SB）的稳定衍生物。该项目的里程碑之一将是其（电子）结构的投资：由于BI的较大且弥漫性的原子轨道，Bismaaromatamatomatantals系统以及开放式壳透明式的DiradAdicaloid形式显得合理，其较大的原子半径也可能允许经过跨性别的BIBI键合，从而导致生物学结构的基础。封闭壳结构的单线 - 三曲线能隙将进行研究。在碳框架下由笨重的亚物质引起的空间障碍将沿BI原子替代分子间二聚化。靶化合物对氢，一氧化碳，二氧化碳，烷烃和炔烃等小分子的反应性将进行研究，旨在在（混合）（混合）二核pnicticen diradical（OIDS）中建立和合理化过渡金属样行为。本文靶向的化合物将通过自由基途径测试作为脱氢E键形成（E = N，P）的新型催化剂。