M@B9 and M@B10 molecular wheels containing planar nona- and deca-coordinate heavy group 11, 12, and 13 metals (M=Ag, Au, Cd, Hg, In, Tl)

Abstract

A density functional and ab initio theory investigation on M@B 9 and M@B 10 molecular wheels containing planar nona-and deca-coordinate heavy group 11, 12 and 13 metals (M=Ag, Au, Cd, Hg, In, Ti) has been performed. These unusual clusters all prove to be true minima on the potential energy surfaces of the systems and σ+π double aromatic in nature. The first two vertical one-electron detachment energies of M@B 1 − 0 (M=Ag, Au) anions and first two ionization potentials of M@B 9 (M=Ag, Au) and M@B 10 (M=Cd, Hg) neutrals were calculated to aid future experiments. The cluster complexes designed in this work may expend the domain of planar hyper-coordinate elements to include heavy group 11, 12, and 13 metals and serve as interesting candidates to be targeted in experiments.planar hyper-coordinate, heavy metals, density functional theory, ab initio, geometries, electronic structures

Observation of the Highest Coordination Number in Planar Species: Decacoordinated Ta©B10− and Nb©B10− Anions

“…[38] Molekel 5.4.0.8 was used for MO visualization. [39] Received: November 9, 2011 Revised: December 30, 2011 Published online: January 20,2012 . Keywords: ab initio calculations · aromaticity · coordination modes · hypercoordination · photoelectron spectroscopy…”

“…[18] The quest for higher coordination numbers was limited primarily to theoretical calculations. [12,20,21] The highest coordination number considered computationally was ten for a broad range of metal atoms: CB 10 2+ , SiB 10 2+ , GeB 10 2+ , SnB 10 2+ , PbB 10 2+ , [12] AuB 10 À , AgB 10 À , CdB 10 , HgB 10 , InB 10 + , TlB 10 + , [20] and ScB 10 3À , TiB 10 2À , VB 10 À , FeB 10 2+ , NiB 10 2+ , CuB 10 3+ , CuB 10 À , ZnB 10 . [21] Though some of these proposed species satisfy our electronic design principle, none was known to be the global minimum.…”

MB 8 2− (M = Be, Mg, Ca, Sr, and Ba): Planar octacoordinate alkaline earth metal atoms enclosed by boron rings

“…Apart from carbon, many other planar hypercoordinate main group elements have also been reported, including planar hypercoordinate boron by Wang et al [33] and planar hypercoordinate silicon by Li et al [34]. Very recently, planar hypercoordinate transition metals, e.g., Fe, Co, Ni, Au, Sc and Zn have also been investigated [35][36][37][38][39][40][41][42]. A systematic study of planar hypercoordinate molecules with first row d-block metal atoms in the center of boron rings was carried out in our earlier computational work [43,44].…”

B19−: An Aromatic Wankel Motor

“…In the last ten years, several boron wheels with maingroup elements [8][9][10][11][12][13][14] or transition-metal atoms [15][16][17][18] at the ring center have been proposed theoretically. In 2005, Erhardt et al studied some aromatic boron wheels (C 2 B 8 , C 3 B 9 3+ , and C 5 B 11 + ) with more than one carbon at the center (Figure 2).…”