Spiro Metalla-aromatics of Pd, Pt, and Rh: Synthesis and Characterization
Spiro Metalla-aromatics of Pd, Pt, and Rh: Synthesis and Characterization
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Pd、Pt 和 Rh 的螺环金属芳烃：合成和表征
DOI：
10.1021/jacs.7b02039
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发表时间：
2017-04-12
影响因子：
15
通讯作者：
Xi, Zhenfeng
中科院分区：
文献类型：
--
作者：
Zhang, Yongliang;Wei, Junnian;Xi, Zhenfeng
由于芳香性的概念代表了化学中最基本的原则之一，因此，对前所未有的令人兴奋的芳香体系的研究继续推动着这一领域的研究。本文中，我们报告的合成和表征螺环金属-芳香族化合物，其中过渡金属（Pd，Pt，或Rh）是螺原子，交叉共轭两个芳香族五元金属杂环。这些螺环金属-芳族化合物倾向于采取正方形平面几何形状，其中二面角受到α-位取代基之间的空间排斥的影响。通过两种实验测量（X射线结构分析、NMR光谱、XPS等）进行表征和分类。和理论分析（DFT计算，伊势，AICD，NICS和CMO），所有这些基本的观察扩展了芳香性和有机金属化学的概念。
Since the concept of aromaticity represents one of the most fundamental principles in chemistry, the search for unprecedented and exciting aromatic systems, therefore, continues to drive research in this area. Herein we report the synthesis and characterization of Spiro metalla-aromatics, in which the transition metal (Pd, Pt, or Rh) is the Spiro atom, that cross-conjugates two aromatic five-membered metallacycles. These Spiro metalla-aromatics tend to take square planar geometries, with the dihedral angle being influenced by the steric repulsion between the alpha-positioned substituents. Rationalized and classified via both experimental measurements (X-ray structural analysis, NMR spectroscopy, XPS, etc.) and theoretical analysis (DFT calculation, ISE, AICD, NICS, and CMOs), all these fundamental observations extend the concept of aromaticity and organometallic chemistry.