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Synthesis, Spectroscopic and Structural Characterization of Novel Diiodine Adducts with the Heterocyclic Thioamides, Thiazolidine-2-thione (tzdtH), Benzothiazole-2-thione (bztzdtH) and Benzimidazole-2-thione (bzimtH)

“…Thus, the agents should be able to form stable complexes with diiodine, diverting iodides from their second oxidation step (I 2 Ǟ 2 I ϩ ϩ 2 e Ϫ ) and in this way prevent the electrophilic substitution of I ϩ on the tyrosine residue of thyroglobulin. [2c,43] This conclusion seems to be substantiated in our work, because (i) like methimazole, [9] thiazolidine-2-thione forms the most stable complexes with I 2 in CH 2 Cl 2 solution, compared with the other two ligands [8,9,22] assuming the formation of 1:1 complexes; (ii) the data shows that thiazolidine-2-thione can be classified as a strong donor ligand, in contrast to the non-anti-thyroidal activity of the two other ligands; (iii) thiazolidine-2-thione is such a strong donor that it causes heterolytic cleavage of the diiodine molecule to form [{D 2 I ϩ }I 3 Ϫ ·2I 2 ] species and is able to carry two more neutral I 2 molecules in the solid state, which the two other ligands cannot.…”

“…The ligands bztzdtH (II) and bzimtH (III), on the other hand, were also used for comparison purposes. Formation constant measurements of all these ligands with diiodine have been reported previously [8,9,21,22] in organic solvents, but always assuming the formation of 1:1 complexes in solution. No structural and/ or spectroscopic studies have ever been reported previously.…”

Hypervalent Adducts of Chalcogen-Containing peri-Substituted Naphthalenes; Reactions of Sulfur, Selenium, and Tellurium with Dihalogens

“…15,22 Ionic compounds, often accompanied by counteranions of polyhalides adopting unusual and sometimes complex structures are also known. 15,22,24,25,26,27,28,29,30,31,32,33 The neutral charge-transfer (C.-T.) "spoke" adduct (R 2 E-X-Y, 8-E-3) and the "seesaw" (X-ER 2 -Y, 10-E-4) insertion adduct, characteristic of quasi-linear hypervalent E-X-Y 15,22,28,34,35 and X-E-Y 14,15,22,28,31,36,37 fragments respectively are the most common structural motifs generated from the reaction of diorganochalcogen-donors [R 2 E] with inter-or dihalogens.…”

Synthesis, coordination properties, and analytical applications of mixed donor macrocycles containing the 1,10-phenanthroline sub-unit

“…In all cases, an [N 2 S 3 + L'] distorted octahedral coordination is observed at the metal centre with the macrocyclic ligand always adopting the typical locked-folded conformation [35,40,41]. [42]. Therefore, the complex cation [Ni(L 1 )(MeCN)] 2+ acts as template of the two different polyiodide networks based on interacting I 3 -/I 5 -and I 5 -/I 7 -, respectively.…”