Synthesis, structural characterization, and computational studies of novel diiodine adducts with the heterocyclic thioamides N-methylbenzothiazole-2-thione and benzimidazole-2-thione: Implications with the mechanism of action of antithyroid drugs
Φόρτωση...
Ημερομηνία
Συγγραφείς
Corban, G. J.
Hadjikakou, S. K.
Hadjiliadis, N.
Kubicki, M.
Tiekink, E. R. T.
Butler, I. S.
Drougas, E.
Kosmas, A. M.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Inorg Chem
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
Reaction of N-methylbenzothiazole-2-thione (C8H7NS2 or NMBZT) with diiodine produced the charge-transfer (ct) complex [(NMBZT) (.) I-2(1). NMBZT reacts with diiodine in the presence of FeCl3 in a molar ratio of 3:6:1 and forms the ionic complex {[(NMBZT)(2)I+]center dot[FeCl4](-)] (2) together with {[(NMBZT)(2)I(+)center dot[I-7](-)} (2a) iodonium salt. The reaction of benzimidazole-2-thione (C7H6N2S or MBZIM) with diiodine on the other hand results in the formation of the ct {[(MBZIM)I-2](+)[I-3](-)}center dot[(MBZIM)center dot I-2] (3) compound. The compounds have been characterized by elemental analyses, DTA-TG, FT-Raman, FT-IR, UV-vis, and H-1 NMR spectroscopies, and X-ray crystal structure determinations. Compound 1, C8H7I2NS2, is orthorhombic with a space group Pna2(1) and a = 12.5147(13) angstrom, b = 22.536(3) angstrom, c = 4.2994(5) angstrom, and Z = 4. Compound 2, C16H14Cl4FeIN2S4, is monoclinic, space group C2/c, a 35.781(2) angstrom, b = 7.4761(5) angstrom, c = 18.4677(12) angstrom, beta = 107.219(1)degrees, and Z = 8. Compound 3, C21H18I6N6S3, monoclinic, space group P2(1)/n, a = 14.0652(11) angstrom, b = 22.536(3) angstrom, c = 4.2994(5) angstrom, beta = 99.635(7)degrees, and Z = 4, consists of two component moieties cocrystallized, one neutral which contains the benzimidazole-2-thione (MBIZM) ligand bonded with an iodine atom through sulfur, forming a compound with a "spoke" structure [(MBZIM)I-2] 3a, while the other is the ionic complex {[(MBZII)(2)I+}center dot[I-3](-)} (3b). The X-ray crystal structure of 1 shows a bond between the thione-sulfur atom and one of the iodine atoms in an essentially planar arrangement. In the cation of 2, an iodine is coordinated by two thione-sulfur atoms in a linear arrangement but the molecule is not planar. For the first time in the solid state a spoke-ionic mixed complex has been characterized in 3. One component of the structure is a molecular diiodine adduct, i.e., [(MBZIM)I-2] (3a), with a linear coordination geometry in a decidedly planar arrangement, and the other component is an ionic adduct {[(MBZIM)(2)I](+)center dot[I-3](-)] (3b) with the cation having an arrangement similar to that found for 1. Theoretical calculations using density functional (DFT) and ab initio Hartree-Fock theory have been carried out for I and 3a,b. The results are consistent with the experimental data. Conclusions on the behavior of a thioamide, when used as an antithyroid drug, have also been made.
Περιγραφή
Λέξεις-κλειδιά
i iodothyronine deiodinase, charge-transfer adducts, ray crystal-structures, x-ray, molecular-complexes, iodine monobromide, thyroid peroxidase, ft-raman, oxidation, thiones
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000233180600060
http://pubs.acs.org/doi/pdfplus/10.1021/ic0484396
http://pubs.acs.org/doi/pdfplus/10.1021/ic0484396
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας