一种空间分离的细菌烯-碳素化合物,用于选择性小分子激活.
Mingdong Zhong1, Zheng Su1, Xiaohui Jiang1
1Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
合成了一种新的细菌烯-碳化合物,并证明了选择性小分子激活. 反应性取决于反应剂,碳位激活电友和细菌位与酸盐反应.
科学领域:
- 有机金属化学 有机金属化学
- 主群 化学 化学
- 碳和基烯的化学结构
背景情况:
- N-异环碳 (NHCs) 是多功能联体和反应性物种.
- 细菌烯是碳的类型,具有独特的反应性.
- 含有细菌烯和碳基分组的化合物很少见,限制了对它们联合反应性的研究.
研究的目的:
- 合成和表征一个空间分离的细菌烯-碳化合物.
- 为了研究这种双功能分子的选择性反应性.
- 探索其在小分子激活中的潜力.
主要方法:
- 一个 (amidinato) 甲基烯和一个deprotonated N- heterocyclic carbene.之间的盐去除反应.
- 使用光谱技术和X射线衍射进行表征.
- 与各种小分子 (异酸盐,异酸盐,BH3·SMe2,GeCl2·二氧化,S8,梅西化) 的反应.
- 密度函数理论 (DFT) 的计算和自然人口分析 (NPA).
主要成果:
- 成功合成和表征细菌烯-碳化合物 (1).
- 证明了选择性小分子激活:碳中心与异酸盐,异酸盐,BH3·SMe2和GeCl2·二氧化反应.
- 细菌烯中心选择性地与梅西他化物反应,形成imidogermane.
- 在两个中心观察到S8和BH3·SMe2的双重加法产物.
- DFT计算揭示了影响反应性的电子性质:HOMO在碳基碳上,HOMO-2在Ge单双上,LUMO在Ge4p轨道上.
结论:
- 合成的细菌烯-碳化合物表现出可调节的,选择性反应性.
- 电子结构决定了在碳或细菌中心的优先激活.
- 这项工作扩大了双功能主要组化合物及其在小分子激活中的应用范围.
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