Structural motifs of diiodine complexes with amides and thioamides

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Parigoridi, I. E.
Corban, G. J.
Hadjikakou, S. K.
Hadjiliadis, N.
Kourkoumelis, N.
Kostakis, G.
Psycharis, V.
Raptopoulou, C. P.
Kubicki, M.

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Royal Society of Chemistry

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peer reviewed

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Dalton Transactions

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The reaction of 2-pyrimidone hydrochloride ([C(4)H(5)N(2)O](+)[Cl](-) or [PMOH(2)](+)[Cl](-)) with diiodine in a dichloromethane-methanol solution resulted in the formation of ([C(4)H(5)N(2)O](+))(2)[I(2)Cl(2)](2-) (1) complex. The compound was characterized by elemental analysis, FT-IR, DTA-TG and conductivity titrations. The crystal structure of 1 was also determined by X-ray diffraction at 294(1) K. Compound 1 is monoclinic, space group P2(1)/n, consisting of two cationic [PMOH(2)](+) species and a [I(2)Cl(2)](2-) counter dianion. The cation is in its keto form. Direct reaction of thiazolidine-2-thione (tzdtH), with diiodine in dichloromethane solution, on the other hand, led to the formation of a crystalline solid which contained two complexes of formulae [(tzdtH)(2)I](+)[I(3)](-)center dot 2I(2) (2) and [(tzdtH)I(2)](2)center dot I(2) (2a) in a ratio of 90 to 10%. Complex 2a was characterized by X-ray analysis at 180(2) K. Compound 2a is monoclinic, space group C2/c and contains two units of [(tzdtH)I(2)] "spoke" structures. Compound 1, as well as the known species iodonium salt [(tzdtH)(2)I](+)[I(3)](-)center dot 2I(2) (2) and the charge transfer (CT) iodine complexes of formulae [(bztzdtH)I(2)] (3) and [(bztzdtH)I(2)]center dot I(2) (4) (bztzdtH = 2-mercaptobenzothiazole) with "spoke" and extended "spoke" structures respectively, were tested for their oxidizing activity towards 3,5-di-tert-butylcatechol to 3,5-di-tert-butyl-o-benzoquinone.

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x-ray characterization, charge-transfer complexes, antithyroid drugs, iodothyronine deiodinase, heterocyclic thioamides, crystal-structure, transfer adducts, oxidation, iodine, mechanism

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<Go to ISI>://000259411500008
http://pubs.rsc.org/en/content/articlepdf/2008/dt/b805825c

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en

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Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας

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