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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
A tris-spiro metalla-aromatic system featuring Craig-Möbius aromaticity
Zhe Huang1, Yongliang Zhang1, Wen-Xiong Zhang1
1Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
Abstract:
As aromaticity is one of the most fundamental concepts in chemistry, the construction of aromatic systems has long been an important subject. Herein, we report the synthesis and characterization of a tris-spiroaromatic complex, hexalithio spiro vanadacycle 2. The delocalization of the four electrons within the two V 3d orbitals and the π* orbitals of the three biphenyl ligands leads to a 40π Craig-Möbius aromatic system with three metalla-aromatic rings, as revealed by both experimental measurements and theoretical analyses. For comparison, if Cr is used instead of V, a similar Craig-Möbius aromatic system can not be generated. In this case, pentalithio spiro chromacycle 3 is obtained, and the Cr center uses its two 3d orbitals to form two independent metalla-aromatic rings. This work presents a type of aromatic systems that will contribute to both aromaticity theory and organometallic chemistry.
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