Observation of Möbius Aromatic Planar Metallaborocycles

Abstract

Möbius aromaticity was developed for twisted annulenes with electron counting rules opposite to those of Hückel aromaticity. The introduction of transition metals makes it possible for <i>planar</i> cyclic systems to exhibit Möbius aromaticity. Here we report the first planar monocyclic metallaboron systems with Möbius aromaticity. The structures and bonding of two rhenium-boride clusters are studied by high-resolution photoelectron imaging and ab initio calculations. The ReB₃^- cluster is shown to have a near-pyramidal structure, while ReB₄^- is found to be a planar pentagonal ring. Chemical bonding analyses show that both ReB₄^- and ReB₄ possess four delocalized π-electrons, including two π-electrons in an orbital of Möbius topology. NICS calculations reveal strong aromatic characters in ReB₄^- and ReB₄, consistent with the 4<i>n</i> electron counting rule for Möbius aromaticity.