The Peculiar Role of the Au3 Unit in Aum, Clusters: σ-Aromaticity of the Au5Zn+ Ion

作者：Li, Yanle; Oliveira, Vytor; Tang, Chunmei; Cremer, Dieter^*; Liu, Chunyan; Ma, Jing^*

来源：Inorganic Chemistry, 2017, 56(10): 5793-5803.

DOI：10.1021/acs.inorgchem.7b00404

• EFFECTIVE CORE POTENTIALS
• THEORETICAL DETERMINATION
• MOLECULAR CALCULATIONS
• DENSITY FUNCTIONALS
• PERTURBATION-THEORY
• RING
• CONFORMATION
• RANGE
• THERMOCHEMISTRY
• CYCLOPROPANE

The stability of small Au-m (m = 47) clusters is investigated by analyzing their energetic, geometric, vibrational, magnetic, and electron density properties. Gold clusters can be constructed from stable cyclic 3-center-2-electron (3c-2e) Au-3(+) units (3-rings) with sigma-aromaticity. The stabilization requires a flow of negative charge from internal 3-rings with electron-deficient bonding to peripheral 3-ring units with stronger AuAu bonds. The valence-isoelectronic clusters Au6 and Au5Zn+ have similar electronic properties: Au5Zn+ is a strongly s-aromatic molecule. An understanding of the structure of Aum clusters is obtained by deriving a Clars Rule equivalent for polycyclic gold clusters: The structure with the larger number of rings with dominant 3c-2e character and a smaller degree of 3c-3e character occupies the global minimum of the Aum potential energy surface.

• 出版日期2017-5-15
• 单位南京大学