Re©B₈^– and Re©B₉^–: New Members of the Transition-Metal-Centered Borometallic Molecular Wheel Family

Abstract

Transition-metal-centered monocyclic boron wheel clusters (M©B _n ^q) represent a family of interesting borometallic compounds with double aromaticity. A variety of early and late transition metal atoms have been found to form such structures with high symmetries and various B _n ring sizes. Here we report a combined photoelectron spectroscopy and quantum-chemistry theoretical study of two M©B _n^- clusters from the middle of the transition metal series: Re©B₈^- and Re©B₉^-. Global minimum structure searches revealed that ReB₈^- adopts a pseudo- C_{8 v} structure while ReB₉^- is a perfectly planar D_{9 h} molecular wheel. Chemical bonding analyses showed that both clusters exhibit σ and π double aromaticity and obey the electronic design principle for metal-centered borometallic molecular wheels. The central Re atoms are found to possess unusually low oxidation states of +I in Re©B₈^- and +II in Re©B₉^-, i.e., the Re atom behaves similarly to late transition metal elements (Ru, Fe, Co, Rh, Ir) in the M©B _n^- molecular wheels. These two clusters become new members of the family of transition-metal-centered monocyclic borometallic molecular wheels, which may be viable for chemical syntheses with appropriate ligands.