Rhodapentalenes: Pincer Complexes with Internal Aromaticity
Qingde Zhuo,
Hong Zhang,
Linting Ding,
Jianfeng Lin,
Xiaoxi Zhou,
Yuhui Hua,
Jun Zhu,
Haiping Xia
Affiliations
Qingde Zhuo
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Hong Zhang
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Linting Ding
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Jianfeng Lin
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Xiaoxi Zhou
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Yuhui Hua
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Jun Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Haiping Xia
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China; Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055, China; Corresponding author
Summary: Pincer complexes are a remarkably versatile family benefited from their stability, diversity, and tunability. Many of them contain aromatic organic rings at the periphery, and aromaticity plays an important role in their stability and properties, whereas their metallacyclic cores are not aromatic. Herein, we report rhodapentalenes, which can be viewed as pincer complexes in which the metallacyclic cores exhibit considerable aromatic character. Rhodapentalenes show good thermal stability, although the rhodium-carbon bonds in such compounds are fragile. Experimental and computational studies suggest that the stabilization of rigid CCC pincer architectures together with an intrinsic aromaticity is vital for these metallacyclic rhodium species. Dearomatization-aromatization reactions, corresponding to metal-ligand cooperation of classical aromatic pincer complexes, were observed in this system. These findings suggest a new concept for pincer chemistry, the internal aromaticity involving metal d-orbitals, which would be useful for exploiting the nature of construction motif and inspire further applications. : Chemistry; Inorganic Chemistry; Organometallic Chemistry Subject Areas: Chemistry, Inorganic Chemistry, Organometallic Chemistry
