State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
Angew Chem Int Ed Engl. 2015 Jun 8;54(24):7189-92. doi: 10.1002/anie.201502412. Epub 2015 Apr 27.
The synthesis of small cyclic metal carbynes is challenging due to the large angle strain associated with the highly distorted nonlinear triple bonds. Herein, we report a general route for the synthesis of five-membered cyclic metal carbyne complexes, osmapentalynes, by the reactions of an osmapentalene derivative with allene, alkyne, and alkene. Experimental observations and theoretical calculations document the aromaticity in the fused five-membered rings of osmapentalynes. The realization of transforming osmapentalene to osmapentalyne through this general route would not only allow further exploration of metallapentalyne chemistry but also show promising applications of this novel aromatic system with broad absorption band and high molar absorption coefficient.
由于高度扭曲的非线性三键所带来的大角度应变，小环金属卡宾的合成具有挑战性。在此，我们报告了一种通过薁五烯衍生物与丙二烯、炔烃和烯烃反应合成五元环金属卡宾配合物，薁五炔的一般方法。实验观察和理论计算证明了薁五炔中稠合五元环的芳香性。通过这条通用路线将薁五烯转化为薁五炔的实现不仅可以进一步探索金属戊二炔化学，而且还展示了这个具有宽吸收带和高摩尔吸光系数的新型芳香体系的广阔应用前景。
