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首页> 外文期刊>Chemistry: A European journal >Regioselective Intramolecular Pauson-Khand Reactions of C_60:An Electrochemical Study and Theoretical Underpinning
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Regioselective Intramolecular Pauson-Khand Reactions of C_60:An Electrochemical Study and Theoretical Underpinning

机译：C_60的区域选择性分子内Pauson-Khand反应：电化学研究和理论基础

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摘要

Suitably functionalized fullero-pyrrolidines endowed with one or two propargyl groups at the C-2 position of the pyrrolidine ring(1,6-enynes)react efficiently and regioselectively with [Co_2(CO)_8] to afford the respective Pauson-Khand products with an unprecedented three(5a-d,7,and 24)or five(25)pentagonal rings,respectively,fused onto the fullerene sphere.Fullero-pyrrolidines with 1,7-,1,9-,1,10-,or 1,11-enyne moieties do not undergo the PK reaction and,instead,the intermediate dicobalt complexes formed with the alkynyl group are isolated in quantitative yields.These differences in reactivity have been studied by DFT calculations with a generalized gradient approximation(GGA)functional and several important energy and structural differences were found for the intermediates formed by the interaction between the coordinatively unsaturated Co atom and the pi system of C_60 in 1,6-and 1,7-enynes.The different lengths of the alkyne chains are responsible for the observed reactivities.Cyclic voltammetry reveals that the presence of the cyclopentenone's car-bonyl group connected directly to the C_60 core results in PK compounds with remarkable electron-accepting ability.
机译：在吡咯烷环（1,6-烯炔）的C-2位置带有一个或两个炔丙基的适当官能化的全吡咯烷酮可以与[Co_2（CO）_8]进行区域选择性反应，从而分别提供具有以下特征的Pauson-Khand产品：前所未有的三个（5a-d，7和24）或五个（25）五角形环稠合在富勒烯球上。具有1,7-，1,9-，1,10-或1的富勒并吡咯烷，11-烯炔部分不进行PK反应，而是以定量收率分离了与炔基形成的中间二甲杂醇配合物。这些反应性的差异已通过DFT计算进行了研究，并采用了广义梯度近似（GGA）的功能和对于在1,6-和1,7-烯炔中的配位不饱和Co原子与C_60的pi体系之间的相互作用形成的中间体，发现了一些重要的能级和结构差异。观察到的反应性ic伏安法表明，直接连接到C_60核的环戊烯酮的羰基基团的存在会导致PK化合物具有出色的电子接受能力。

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