通过分子间Zr(IV) - 素挫折的易斯对激活小分子
Owen J Metters1, Sebastian J K Forrest1, Hazel A Sparkes1
1School of Chemistry, University of Bristol , Cantock's Close, Bristol BS8 1TS, United Kingdom.
Journal of the American Chemical Society
|January 21, 2016
概括
新的分子间过渡金属丧的易斯对 (FLPs) 激活D2和CO2等小分子. 这些系统提供可调节的特性,并通过DOSY NMR揭示易斯酸/相互作用.
科学领域:
- 有机金属化学
- 催化剂
- 超分子化学
背景情况:
- 丧的易斯对 (FLP) 对于小分子激活至关重要.
- 在此之前,只有分子内FLPs表现出广泛的反应性.
- 分子间FLP在固态和电子特性方面具有更高的调整性.
研究的目的:
- 开发和描述新的分子间过渡金属FLP.
- 探索这些新FLP的小分子激活能力.
- 研究固体和电子因素对FLP反应性和选择性的影响.
主要方法:
- 合成了10种新的基于酸和酸的分子间FLPs.
- 与包括D2,CO2,THF和PhCCH在内的小分子发生反应.
- 用DOSY核磁共振光谱来阐明易斯酸相互作用.
主要成果:
- 与D2,CO2,THF和PhCCH进行广泛的小分子激活化学反应.
- 成功合成了10种具有可调节性质的新型分子间过渡金属FLPs.
- 发现具有较小托尔曼硬质参数的素产生高度反应和选择性的FLPs.
- 使用DOSY NMR在这些系统中的易斯酸/相互作用提供了首次见解.
结论:
- 分子间FLP可以实现广泛的小分子激活,与分子内系统相竞争.
- 路易斯基组件的系统变化可以微调FLP的反应性和选择性.
- 较小的酸体量提高了过渡金属FLP的反应性和选择性.
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