Unusual 4-membered ring strained metalla-cycloallenes of the early transition metals Titanium, Zirconium and Hafnium

早期过渡金属钛、锆和铪的不寻常的四元环应变金属-环联烯

• 批准号: 181753120
• 负责人: Professor Dr. Uwe Rosenthal
• 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
• 财政年份: 2010
• 资助国家: 德国
• 起止时间: 2009-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/181753120?language=en
• 关键词: Unusual; membered; ring; strained; metalla

The result of this project should be unusual metallacycles of the early transition metals Titanium, Zirconium and Hafnium to find the limitations for the existence of such ring-strained systems for the example of unusual 4-membered metalla-cycloallenes. As such unusual 5-membered metallacycles exist metallacyclocumulenes (1-metallacyclopenta-2,3,4-trienes), metallacyclopentynes (1-metallacyclopenta-3-ynes) and metallacycloallenes (1-metallacyclopenta-2,3-dienes) odf the metals Ti, Zr and Hf,. whereas the smaller 4-rings like metallacycloallenes (1-metallacyclo-buta-2,3-dienes) are unknown for these metals. The synthesis of such compounds is interesting, because - like for the 5-membered metallacyclen - a general better knowledge of synthetical and theretical aspects for such organometallic compounds is expected which is relevant for catalytic C-C coupling reactions in the future. One can understand the compounds which were obtained during the last years are (as a result of other supported DFG-projects) better regarding the bonding situation because they were studied theoretically. The unexpected stability together with the chemical inertness was a part of the basic project and should be extended into two directions: - 5-membered hetero-metallacyclocumulenes and hetero-metallacycloalkynes - 4-membered all-C-metallacycles like metallacycloallenes (1-metallacyclo-buta-2,3-dienes) and corresponding 4-membered hetero-metallacycles Whereas in the basic project an extension to the hetero atoms such as N, P, O, S for such unusual ring systems was very well investigated by using hetero-butatrienes like R2C=C=C=X, X=C=C=X; X = O, S or R2C=C=C=XR, RX=C=C=XR; X = N, P, the new investigations of this project are concentrated to the synthesis of other 1-metalla-dihetero-cyclo-buta-2,3-dienes, of 1-metalla-monohetero-cyclo-buta-2,3-dienes and (by using the theoretical results of the basic project) and new synthetical methoids again to 1-metalla-all-C-cyclo-buta-2,3-dienes.

本项目的结果应该是早期过渡金属钛、锆和铪的异常金属环，以异常的四元金属环烯为例，找出这种环应变体系存在的局限性。这种不寻常的五元金属环存在于金属Ti、Zr和Hf的金属环烯（1-金属环五-2,3,4-三烯）、金属环戊烯（1-金属环五-3-炔）和金属环烯（1-金属环五-2,3-二烯）。而较小的4环，如金属环烯（1-金属环-丁基-2,3-二烯）是未知的这些金属。这类化合物的合成是有趣的，因为-就像5元金属环一样-期望对这类有机金属化合物的合成和理论方面有更好的了解，这与未来催化C-C偶联反应有关。我们可以理解，在过去几年中获得的化合物（作为其他支持的dfg项目的结果）在键合情况方面更好，因为它们是理论上研究的。意想不到的稳定性和化学惰性是基础工程的一部分，应该扩展到两个方向：- 5人hetero-metallacyclocumulenes和hetero-metallacycloalkynes 4-membered all-C-metallacycles像metallacycloallenes (1-metallacyclo-buta-2 3-dienes)和相应4-membered hetero-metallacycles而在基本项目的扩展等杂原子N, P, O,这种不寻常的环系统很好调查使用hetero-butatrienes像R2C = C = C = X, X = C = C = X;X= 0， S或R2C=C=C=XR， RX=C=C=XR；X = N， P，本项目的新研究集中在其他1-金属-二杂环-丁烯-2,3-二烯的合成、1-金属-单杂环-丁烯-2,3-二烯的合成以及（利用基础项目的理论结果）1-金属-全c -环-丁烯-2,3-二烯的合成和新的合成方法上。