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Results of ab initio self-consistent-held (SCF) and density functional theory (DFT) calculations of the gas-phase structure, acidity (free energy of deprotonation, DeltaG(o), and aromaticity of 1,2-diseleno-3,4-dithiosquaric acid (3,4-dithiohydroxy-3-cyclobutene-1,2-diselenone, H2C4Se2S2) are reported. The global minimum found on the potential energy surface of 1,2-diseleno-3,4-dithiosquaric acid presents a planar conformation. The ZZ isomer was found to have the lowest energy among the three planar conformers and the ZZ and ZE isomers are very close in energy. The optimized geometric parameters exhibit a bond length equalization relative to reference compounds, cyclobutanediselenone, and cyclobutenedithiol. The computed aromatic stabilization energy (ASE) by homodesmotic reaction (Eq 1) is -20.1 kcal/mol (MP2(fu)/6-311+G**//RHF/6-311+G**) and -14.9 kcal/mol (B3LYP//6-311+G**//B3LYP/6-311+G**). The aromaticity of 1,2-diseleno-3,4-dithiosquaric acid is indicated by the calculated diamagnetic susceptibility exaltation (A) -17.91 (CSGT(IGAIM)-RHF/6-311+G**//RHF/6-311+G**) and -31.01 (CSGT(IGAIM)-B3LYP/G-311+G**// B3LYP/6-311+G**). Thus, 1,2-diseleno-3,4-dithiosquaric acid fulfils the geometric, energetic and magnetic criteria of aromaticity. The calculated theoretical gas-phase acidity is DeltaG(1(298K))(o) = 302.7 kcal/mol and DeltaG(2(298K))(o) = 388.4 kcal/mol. Hence, 1,2-diseleno-3,4-dithlosquane acid is a stronger acid than squaric acid(3,4-dihydroxy-3-cyclobutene-1,2-dione, H2C4O4).
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THEORETICAL CHEMISTRY ACCOUNTS
ISSN: 1432-881X
Year: 2000
Issue: 1
Volume: 105
Page: 86-92
2 . 2 6 3
JCR@2000
1 . 6 0 0
JCR@2023
ESI Discipline: CHEMISTRY;
JCR Journal Grade:1
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 3
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