Tetralithio Metalla-aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro-fused by One Manganese Atom.

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 MnCl2 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 6 pi 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.