Structural motifs of diiodine complexes with amides and thioamides.
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)](-).2I(2) (2) and [(tzdtH)I(2)](2).I(2) (2a) in a ratio of 90 to 10%. Complex 2a was characterized by X-ray analysis at 180(2) K. Compound 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)](-).2I(2) (2) and the charge transfer (CT) iodine complexes of formulae [(bztzdtH)I(2)] (3) and [(bztzdtH)I(2)].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.
Parigoridi
Ioanna-Efpraxia
IE
Section of Inorganic and Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina, Greece.
Corban
Ghada J
GJ
Hadjikakou
Sotiris K
SK
Hadjiliadis
Nick
N
Kourkoumelis
Nikolaos
N
Kostakis
George
G
Psycharis
Vassilis
V
Raptopoulou
Catherine P
CP
Kubicki
Maciej
M
D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D007202:Indicators and Reagents; D017613:Iodine Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D017550:Spectroscopy, Fourier Transform Infrared; D013854:Thioamides / Q000737:chemistry*
D000577:Amides; D007202:Indicators and Reagents; D017613:Iodine Compounds; D013854:Thioamides