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author:

Zhou, LX (Zhou, LX.) [1]

Indexed by:

Scopus SCIE

Abstract:

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).

Keyword:

1,2-diseleno-3,4-dithiosquaric acid ab initio aromaticity density functional theory (DFT) gas-phase acidity

Community:

  • [ 1 ] Fuzhou Univ, Dept Chem, Fujian 350002, Peoples R China

Reprint 's Address:

  • 周立新

    [Zhou, LX]Fuzhou Univ, Dept Chem, Fujian 350002, Peoples R China

Email:

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Source :

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

Cited Count:

WoS CC Cited Count:

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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