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Conformational study of the structure of free 12-thiacrown-4 and some of its cation metal complexes

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Abstract

Conformational search of 12-thiacrown-4, 12t4, was performed using the CONFLEX method and the MMFF94S force field whereby 156 conformations were predicted. Optimized geometries of the 156 predicted conformations were calculated at the HF, B3LYP, CAM-B3LYP, M06, M06L, M062x and M06HF levels using the 6-311G** basis set. The correlation energy was recovered at the MP2 level using the same 6-311G** basis set. Optimized geometries at the MP2/6-311G** level and G3MP2 energies were calculated for some of the low energy conformations. The D 4 conformation was predicted to be the ground state conformation at all levels of theory considered in this work. Comparison between the dihedral angles of the predicted conformations indicated that for the stability of 12t4, a SCCS dihedral angle of 180° requirement is more important than a gauche CSCC dihedral angle requirement. Conformational search was performed also for the 12t4–Ag+, Bi3+, Cd2+, Cu+ and Sb3+ cation metal complexes using the CONFLEX method and the CAChe-augmented MM3 and MMFF94S force fields. Conformations with relative energies less than 10 kcal/mol at the MP2/6-31+G*//HF/6-31+G* level, with double zeta quality basis set on the metal cations, were considered for computations at the same levels as those used for free 12t4, using also the 6-311G** basis set. The cc-pVTZ-pp basis set was used for the metal cations. The predicted ground state conformations of the 12t4–Ag+, Bi3+, Cd2+, Cu+ and Sb3+ cation metal complexes are the C 4, C 4, C 4, C 2v and C 4 conformations, respectively. This is in agreement with the experimental X-ray data for the 12t4–Ag+ and Cd2+ cation metal complexes, but experimentally by X-ray, the 12t4–Bi3+ and Cu+ cation metal complexes have C s and C 4 structures, respectively.

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Acknowledgments

Supported by NPST program by King Saud University Project Number: ADV400-02. Adel A. El-Azhary thanks Prof. M. S. El-Shall of the Virginia commonwealth University for hosting him during the summer of 2008 and the use of CDB installed on the University computer system.

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  1. Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Kingdom of Saudi Arabia

    Nada I. Al-Badri, Nada A. Al-Jallal & Adel A. El-Azhary

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  1. Nada I. Al-Badri
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Correspondence to Adel A. El-Azhary.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Al-Badri, N.I., Al-Jallal, N.A. & El-Azhary, A.A. Conformational study of the structure of free 12-thiacrown-4 and some of its cation metal complexes. Theor Chem Acc 130, 919–938 (2011). https://doi.org/10.1007/s00214-011-1043-4

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