title: Unconventional charge distribution in the planar wheel-type M©B6H6(-/0/+) (M = Mn, Fe and Co): central M with negative charges and peripheral boron ring with positive charges.
abstract: Planar wheel-type D6h M©B6H6(-/0/+) (M = Mn, Fe and Co for anion, neutral and cation, respectively.) clusters with a planar hexacoordinate transition-metal at the center of the boron ring were designed and investigated by density functional theory. These planar clusters are chemically stable as a result of their large binding energy, vertical ionization potential, and vertical electron affinity. The detailed natural population and molecular orbital analyses suggest that not only does the M atom donate electrons to the boron ring for participation in the π-delocalized bonding, but also the boron ring donates electrons back to the M atom for the formation of the σ-delocalized bonding, which leads to a strong aromaticity and unconventional charge distribution, i.e., the M atom is negatively charged, while the boron ring is positively charged. This study may open a new area in coordination chemistry for planar hexacoordinate transition metals and we expect further experimental exploration of their synthesis and potential applications.
authors.affiliation: School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, People's Republic of China. houjh163@163.com.
authors.forename: Jianhua
authors.initials: J
authors.lastname: Hou
authors.forename: Qian
authors.initials: Q
authors.lastname: Duan
authors.forename: Jieming
authors.initials: J
authors.lastname: Qin
authors.forename: Xiande
authors.initials: X
authors.lastname: Shen
authors.forename: Jianxun
authors.initials: J
authors.lastname: Zhao
authors.forename: Qingcheng
authors.initials: Q
authors.lastname: Liang
authors.forename: Dayong
authors.initials: D
authors.lastname: Jiang
authors.forename: Shang
authors.initials: S
authors.lastname: Gao