Theoretical Studies of the Gas-phase Acidity and Aromaticity of 3,4-Dithiosquaric Acid

Abstract

Abstract: The conformation, aromaticity and gas phase acidity(free energy of deprotonation, ΔG⁰) of 3,4-dithiosquaric acid(3,4 dimercapto-3-cyclobutene 1,2-dione) were calculated at the SCF and MP₂ and B3LYP levels using 6-311G(d,p) and 6-311+G(d,p) basis sets. The global minimum found on the potential energy surface of 3,4-dithiosquaric acid presents a planar conformation. The ZZisomer was found to be the most stable of the three planar conformers. The aromatic stabilization energy(ASE) and magnetic susceptibility exaltation( Λ ) were also computed by using the homodesmotic reaction and RHF-CSGT(Continues Set of Gauge Transformations) and RHF-IGAIM(a slight variation on CSGT) and B3LYP-CSGT(IGAIM) methods at the 6-311+G(d,p) level. The calculated ASEand Λ were negative values, indicating that 3,4-dithiosqaric acid is aromatic. Thus the titled compound fulfilled the geometrical, energetic and magnetic criteria of aromaticity. The most reliable theoretical gas-phase acidity are ΔG_1,298K⁰ = 1295.4 kJ/mol and ΔG_2,298K⁰ =1691.2 kJ/mol.

Key words: 3,4-Dithiosquaric acid, Ab initio, Density functional theory(DFT), Aromaticity, Gas-phase acidity

CLC Number:

O641.12

TrendMD:

ZHOU Li-Xin, MANG Chao-Yong, HUANG Zun-Xing . Theoretical Studies of the Gas-phase Acidity and Aromaticity of 3,4-Dithiosquaric Acid[J]. Chem. J. Chinese Universities, 2000, 21(4): 596.

References

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