摘要：Since the discovery of the first drum-like cob16- complex, metal-doped drum-like boron nanotubular structures have been investigated with various metal dopants and different tubular size, forming a new class of novel nanostructures. The cob16- cluster was found to be composed of a central co atom coordinated by two fused B8 rings in a tubular structure, representing the potential embryo of metal-filled boron nanotubes and providing opportunities to design one-dimensional metal-boron nanostructures. Here we report improved photoelectron spectroscopy and a more in-depth electronic structure analysis of cob16-, providing further insight into the chemical bonding and stability of the drum-like doped boron tubular structures. Most interestingly, we find that the central co atom has an unusually low oxidation state of ?1 and neutral cob16 can be viewed as a charge transfer complex (co-@BB16+), suggesting both covalent and electrostatic interactions between the dopant and the boron drum.