Affiliation:
1. Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
Abstract
Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi–B–B–Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculations reveal that these ptSi/Ge/Sn/Pb species are the global minima on their potential energy surfaces. Born–Oppenheimer molecular dynamics (BOMD) simulations indicate that XB2Bi2 (X = Si, Ge, Sn, Pb) clusters are robust. Bonding analyses indicate that 20 VEs are perfect for the ptX XB2Bi2 (X = Si, Ge, Sn, Pb): two lone pairs of Bi atoms; one 5c–2e π, and three σ bonds (two Bi–X 2c–2e and one B–X–B 3c–2e bonds) between the ligands and X atom; three 2c–2e σ bonds and one delocalized 4c–2e π bond between the ligands. The ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess 2π/2σ double aromaticity, according to the (4n + 2) Hückel rule.
Funder
National Natural Science Foundation of China
Natural Science Foundation of Shanxi Province
Reference58 articles.
1. Sur Les Formules De Structure Dans L’espace;Arch. Neerl. Sci. Exactes Nat.,1874
2. Sur Les Relations Qui Existent Entre Les Formules Atomiques Des Corps Organiques Et Le Pouvoir Rotatoire De Leurs Dissolutions;Bull. Soc. Chim. Fr.,1874
3. Activation Energy for Interconversion of Enantiomers Containing an Asymmetric Carbon Atom without Breaking Bonds;Monkhorst;Chem. Commun.,1968
4. Planar Tetracoordinate Carbon;Hoffmann;J. Am. Chem. Soc.,1970
5. Stabilization of Planar Tetracoordinate Carbon;Collins;J. Am. Chem. Soc.,1976