研究室工作進展 Nov. 1st, 2013
Coordination-Induced Skeletal Rearrangements of Zirconacyclobutene-Silacyclobutene Fused Complexes
Jing Zhao, Shaoguang Zhang, Wen-Xiong Zhang, and Zhenfeng Xi*
Coord. Chem. Rev. 2013, DOI: http://dx.doi.org/doi:10.1016/j.ccr.2013.08.032
Coordination-induced skeletal rearrangement of transition-metal complexes is of fundamental interest both synthetically and mechanistically. Besides commonly observed ligand substitution, the coordination of ligands may greatly alter the steric and electronic environment around the metal center, thus activating the whole compound, resulting in novel rearrangement or cleavage of chemical bonds. Subsequent formations of chemical bonds would lead to synthetically useful methods for new transition-metal complexes and organic compounds. Zirconacycles have been proved to be very useful for synthetic organic and organometallic chemistry. The present review concentrates on the coordination-induced skeletal rearrangement of zirconacyclobutene-silacyclobutene fused complexes. When treated with nitriles, alkynes, ketones, or other unsaturated organic molecules, the zirconacyclobutene-silacyclobutene fused complexes underwent the coordination-induced rearrangement and new chemical bond forming process, other than the expected direct insertion reactions. Different types of rearrangements were observed depending on the coordinating unsaturated organic molecules. A variety of zirconacycles and organic products were formed efficiently from the zirconacyclobutene-silacyclobutene fused complexes and the unsaturated organic molecules through the coordination-induced rearrangement and new chemical bond forming process.
背景介紹
化學反應活性中間體的分離與結構表征對于理解反應機理具有重要意義，而反應機理研究是化學研究的核心内容之一。通過對活性中間體的結構表征，不僅有助于深入理解反應機理，同時有助于設計新反應，建立新方法，實現新的有機合成方法。金屬雜環化合物是許多重要反應中的中間體。本小組通過合成、分離金屬（如钛、锆、鋁、鎂等）雜五元環以及金屬雜四元環活性中間體，在理解相應反應的機理的同時，利用這些活性中間體，發展了一系列有機合成新方法，合成得到其它方法難于合成的新型金屬有機化合物以及結構多樣的環狀有機化合物。2007年我們應邀在Chem. Soc. Rev. 上系統總結了本實驗室在金屬有機雜化試劑與路易斯酸的“協同效應”研究工作結果（Congyang Wang and Zhenfeng Xi,* Chem. Soc. Rev. 2007, 36, 1395-1406.）。
2011年本小組應邀在Acc. Chem. Res. 上系統總結了本實驗室近十年來在金屬雜環試劑與有機底物的“協同效應”研究方面的工作結果（Wen-Xiong Zhang, Shaoguang Zhang, and Zhenfeng Xi,* Acc. Chem. Res. 2011, 44, 541-551）。該文詳細闡述了一些金屬有機活性中間體與有機底物間的“協同效應”，以及本實驗室“基于機理研究和活性中間體的合成化學”研究理念。
本文應Coord. Chem. Rev.“金屬有機化學前沿”特輯的邀請，從配位化學基本反應的角度，介紹了本實驗室10餘年來開展的锆雜環丁烯并矽雜環丁烯化合物在不同配體的配位誘導作用下發生的一系列骨架重排反應及機理研究結果。