Theoretical Studies on Aromaticity of Spiro Metallaaromatics of (C₁₀H₁₀M)^2‒(M=Ni, Pd, Pt)

Abstract

Aiming to identify the spiro metallaaromatic systems with potential application value, (C₁₀H₁₀M)^2‒(M=Ni, Pd, Pt) derivatives were theoretically investigated. (C₁₀H₁₀M)^2‒-Iso1, which has two 6-membered rings(6MRs) connected by the M spiro atom, is a 14π-aromatic as a whole plane. (C₁₀H₁₀M)^2‒-Iso2 has one 6π-aromatic 5MR and one 10π-aromatic 7MR connected by the spiro atom. The free (C₁₀H₁₀M)^2‒ dianions could not exist due to their rather high frontier orbital energies, while the neutral (C₁₀H₁₀M)Li₂ compounds are extremely stable against dissociation. Since (C₁₀H₁₀M)Li² coumponds are not fully coordinated, they trend to form (C₁₀H₁₀M)Li₄ ²⁺ dications, or even [(C₁₀H₁₀M)Li₂]_n polymers. Arguably, (C₁₀H₁₀M)^2‒ planes are not the only examples for spiro metallaaromaticity, their derivatives are also potential material building blocks.

Keywords

Metalloaromaticity / Metallabenzene / Spiro compound / Inverse sandwich / Through-space NMR shielding(TSNMRS)

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