Can Synthetic All‐Metal Cluster Compound Support Multifold (π and σ) Aromaticity and d‐Orbital Aromaticity?

• Published in: Chinese journal of chemistry Vol. 37; no. 2; pp. 126 - 130
• Main Authors: You, Xue‐Rui, Zhai, Hua‐Jin
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 01.02.2019; Wiley Subscription Services, Inc
• Subjects: Aromaticity; Chemical bonds; Computer applications; Electron clouds; Metal clusters; Organic chemistry; Palladium
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.201800473

Summary of main observation and conclusion There are active debates on whether the concept of aromaticity should be extended beyond carbon based organic systems. One argument against such extension is that the proposed new aromatic species are not bottleable. We present herein in‐depth chemical bonding analyses of a synthetic, core‐shell, intermetalloid [Pd3Sn8Bi6]4‐ cluster. The computational data unravel unprecedented five‐fold (π and σ) aromaticity, including d‐orbital aromaticity. Delocalized electron clouds in this all‐metal system cover the Pd3 core, trigonal pyramid Sn4 caps, peripheral Bi6 ring, and roof‐like Sn2Bi2 walls, each following the (4n + 2) Hückel rule. The present finding is beyond imagination, providing a compelling example that all‐metal aromaticity not only exists in bulk compounds, but also can be in multifold π/σ fashion. Five‐fold aromaticity in a bottleable compound? Chemical bonding analyses reveal that core‐shell D3h [Pd3Sn8Bi6]4‐ cluster possesses five‐fold π/σ aromaticity, including d‐orbital aromaticity.