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Results of ab initio self-consistent-field (SCF) and density functional theory (DFT) calculations of the gas-phase structure, acidity (free energy of deprotonation, DeltaG degrees) and aromaticity of tetraselenosquaric acid (3, 4-difelenyl-3-cy-clobutene-1,2-diselenone, H2C4Se4) are reported. The global minimum found on the potential energy surface of tetraselenosquaric add 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 dose In energy. The optimized geometric parameters exhibit a bond length equalization relative to reference compounds, cyclobutanediselenone, and cyclobutenediselenol. The computed aromatic stabilization energy (ASE) by homodesmotic reaction is -77.4 (MP2(fu)/6 - 311 + G* * //RRF/6 - 311 + G* *) and - 54.8 kJ/mol (B3LYP/6 - 311 + G* * //B3LYP/6 - 311+ G* *). The aromaticity of tetraselenosquaric add is indicated by the calculated diamagnetic susceptibility exaltation (Lambda) - 19. 13 (CSGT(IGAIM) - RHF/6 - 311 + G* * // RHF/6 - 311 + G* * and - 32.91(4 pi (.)10(-6) m(3)/mol)(CSGT(I-GAIM)-B3LYP/6 - 311+ G* * //B3LYP/6 - 311+ G* *). Thus, tetraselenoquaric acid fulfils the geometric, energetic and magnetic criteria of aromaticity. The calculated gas-phase acidity is DeltaG degrees (1(298K)) = 1257.7 and DeltaG degrees (2(298K)) = 1617.1 kJ/mol. Hence, tetraselenosquaric acid is the strongest acid among the three squaric acids (3, 4-dihydroxy-3-cyclobutene-1,2-dione, H2C4O4, 3,4-dihydroxy-3-cyclobutene-1,2-dithione, H2C4S4, 3,4-diselenyl-3-cyclobutene-1,2-diselenane, H2C4Se4).
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CHINESE JOURNAL OF CHEMISTRY
ISSN: 1001-604X
CN: 31-1547/O6
Year: 2000
Issue: 6
Volume: 18
Page: 808-814
0 . 7 0 7
JCR@2000
5 . 5 0 0
JCR@2023
ESI Discipline: CHEMISTRY;
JCR Journal Grade:3
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SCOPUS Cited Count:
ESI Highly Cited Papers on the List: 0 Unfold All
WanFang Cited Count:
Chinese Cited Count:
30 Days PV: 3
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