Stabilization of poly-iodides: structural influences of the cationic disulfides of 2-mercapto-3,4,5,6-tetrahydro-pyrimidine and 2-mercatpo-pyrimidine?

RSC Advances Pub Date: 2012-01-06 DOI: 10.1039/C2RA00013J

Abstract

The reaction of 2-mercapto-3,4,5,6-tetrahydro-pyrimidine (tHPMT) or 2-mercaptopyrimidine (PMTH) with hydroiodic or hydrochloric acids in the presence or absence of di-iodine in dichloromethane solutions resulted in the formation of complexes with formulae [2{(tHPMT)22+} 2(I?) (I42?)] (1), [2{(tHPMT)22+} Cl? 3(I3?)] (2), [6{(tHPMT)22+} 3(Cl?) 2(I?) 5(I3?)] (3) and [2{(PMTH2)+} I42?] (4). The compounds were characterized by FT-IR, and Raman spectroscopic techniques. The crystal structures of 1–4 were also determined by X-ray diffraction. Complexes 1 and 4 contain tetra-iodides di-anions (I42?) as counter parts. The linear geometry of tetra-iodides species is broken in case of 1 and the deviation from the linearity for this di-anion is greater than in any such molecule described thus far. Moreover in complex 3 with a hexa-iodide di-anion, (I62?) is detected by considering the distance of 3.67 ? as a bonding interaction.

Graphical abstract: Stabilization of poly-iodides: structural influences of the cationic disulfides of 2-mercapto-3,4,5,6-tetrahydro-pyrimidine and 2-mercatpo-pyrimidine
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