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Tetralithio Metalla‐aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro‐fused by One Manganese Atom
Author(s) -
Zhang Yongliang,
Wei Junnian,
Zhu Miaomiao,
Chi Yue,
Zhang WenXiong,
Ye Shengfa,
Xi Zhenfeng
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904681
Subject(s) - aromaticity , chemistry , atom (system on chip) , atomic orbital , manganese , crystallography , perpendicular , lithium (medication) , transition metal , computational chemistry , molecule , organic chemistry , physics , medicine , geometry , mathematics , quantum mechanics , computer science , catalysis , embedded system , endocrinology , electron
Abstract Herein, we present the realization of a class of unprecedented aromatic structures 2 : metalla‐aromatics with two independent and perpendicular aromatic rings spiro‐fused by a transition‐metal spiro atom, of which their corresponding organic analogues are impossible. Tetralithio spiro manganacycles 2 are readily synthesized from 1,4‐dilithio‐1,3‐butadienes 1 and MnCl 2 in the presence of lithium. The aromaticity of 2 is supported by experimental measurements (X‐ray structural analysis, NMR) and theoretical analyses (NICS, ACID, MOs). The spiro atom Mn in 2 uses its 3d xz and 3d xy orbitals to form the two perpendicular manganacycles, which are two independent 6π aromatic systems. Theoretical analyses reveal that the Li cations play an indispensable role in governing their geometric and electronic structures and hence their aromaticity. Therefore, this work contributes not only to enrich the concept of aromaticity, but also to deepen the understanding of the fundamental chemical bonding.