Metallacyclobuta-2,3-dienes as organometallic analogs of the smallest cyclic allene – classical metallacyles or unusual transition metal biradcals?

Metallacyclobuta-2,3-diene 作为最小环状丙二烯的有机金属类似物 - 经典金属酰基或不常见的过渡金属双自由基？

• 批准号: 452714985
• 负责人: Professor Dr. Torsten Beweries
• 金额: --
• 依托单位: Leibniz-Institut für Katalyse e. V. an der Universität Rostock (LIKAT)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/452714985?language=en
• 关键词: Metallacyclobuta; dienes; organometallic; analogs; smallest

The project aims at the investigation of synthesis and reactivity of highly unusual metallacyclobuta-2,3-dienes. Based on previous work on an ansa-titanocene system also other group 4 metals, metallocene fragments and allene subtitution patterns will be investigated. One of the main goals is to thoroughly characterise metallacyclobuta-2,3-dienes theoretically and spectroscopically. Previous studies have shown a distinct and unusual biradical character of complex 3. This raises the question whether the reactivity of such compounds is dominated by this phenomenon or whether reactivity patterns found for classical metallacycles occur. The findings of this project will have impact for organometallic chemistry and theoretical inorganic chemistry.The project is composed of the following work packages:- Synthesis of suitable allene precursors (AP1)- Synthesis of new metallacyclobuta-2,3-dienes (AP2)- Spectroscopic and theoretical characterisation of metallacyclobuta-2,3-dienes (AP3)- Reactivity of metallacyclobuta-2,3-dienes (AP4)

该项目旨在研究极不寻常的金属环丁二烯-2,3-二烯的合成和反应性。基于之前对柄型二茂钛系统的研究，我们还将研究其他第 4 族金属、茂金属片段和丙二烯取代模式。主要目标之一是从理论上和光谱上彻底表征金属环丁二烯-2,3-二烯。先前的研究已经表明配合物3具有独特且不寻常的双自由基特征。这提出了这样的问题：此类化合物的反应性是否受这种现象支配，或者是否发生了经典金属环的反应性模式。该项目的研究结果将对有机金属化学和理论无机化学产生影响。该项目由以下工作包组成：-合适的丙二烯前体的合成（AP1）-新型金属环丁二烯-2,3-二烯（AP2）的合成- 2,3-二烯金属 (AP3) 的光谱和理论表征-2,3-二烯金属 (AP4) 的反应性