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.

本项目的目的是分离潜在的双自由基（类）bismanthrene和相关的混合氮族元素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研究它们的（电子）结构：由于Bi的大而弥散的原子轨道，bismaaromatic系统以及开壳diradicaloid形式似乎是合理的，并且其大的原子半径也可能允许transannular Bi-Bi键合，导致双环结构基序。单重态-三重态能隙的封闭壳层结构将进行研究。碳骨架上的大体积取代基引起的空间位阻将抑制分子间沿着Bi原子的二聚。目标化合物对小分子如氢，一氧化碳，二氧化碳，烯烃和炔烃的反应性将进行研究，旨在建立和合理化过渡金属样行为（混合）双核氮族双自由基（oid）s。本文所针对的化合物将作为新型催化剂进行测试，用于通过自由基途径形成双价E-E键（E = N，P）。