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

该项目旨在研究高度不寻常的金属环丁-2，3-二烯的合成和反应性。基于以前对柄型二茂钛体系的研究，还将研究其它第4族金属、茂金属碎片和丙二烯取代模式。主要目标之一是从理论上和光谱上对金属环丁-2，3-二烯进行彻底的研究。以前的研究表明，一个独特的和不寻常的双自由基字符的复杂3。这就提出了一个问题，即这些化合物的反应性是否受这种现象的支配，或者是否发生经典金属杂环的反应性模式。该项目的研究成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：-合成合适的丙二烯前体（AP 1）-合成新的金属环丁-2，3-二烯（AP 2）-金属环丁-2，3-二烯（AP 3）的光谱和理论表征-金属环丁-2，3-二烯（AP 4）的反应性

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)