Copper(I)/(II) or silver(I) ions towards 2-mercaptopyrimidine: An exploration of a chemical variability with possible biological implication (Journal article)

Batsala, G. K./ Dokorou, V./ Kourkoumelis, N./ Manos, M. J./ Tasiopoulos, A. J./ Mavromoustakos, T./ Simcic, M./ Golic-Grdadolnik, S./ Hadjikakou, S. K.

Direct reaction of copper(I) chloride with 2-mercaptopyrimidine (pmtH) in the presence of the triphenylphosphine (tpp) in 1: 1: 2 M ratio forms the mixed ligand Cu(I) complex with formula [CuCl(tpp)(2)(pmtH)] (1). The dimeric {[Cu(tpp)(pmt)](2) 0.5(MeOH)} (2) complex was derived from the reaction of 1 with twofold molar amount of sodium hydroxide. However, the reaction of copper(II) sulfate or nitrate with pmtH and tpp in 1: 2: 2 M ratio, unexpectedly results in the formation of the [CuSH(tpp)(2)(pmtH)] (3) complex. Further studies have shown that the [Cu(tpp)(2)(pmt)] (4) complex is formed by reacting copper(II) acetate with pmtH in the presence of tpp in 1: 2: 2 M ratio, while in the absent of tpp, the Cu(CH3COO)(2) or CuSO4 is found to oxidizes pmtH to its corresponding disulfide (pmt)(2). For comparison the mixed ligand silver(I) chloride or nitrate complexes with formula [AgCl(tpp)(2)(pmtH)] (5) or [Ag(NO3)(tpp)(2)(pmtH)] (6) are also synthesized by reacting of the AgCl or AgNO3 with pmtH and tpp in 1: 2: 2 M ratio. The complexes have been characterized by elemental analyses, m. p., vibrational spectroscopy (mid-, far-FT-IR and Raman), H-1 NMR, UV-Vis, ESI-MS, TG-DTA spectroscopic techniques and single crystal X-ray crystallography at ambient conditions. Photolysis of 1-6, was also studied and the results showed formation of triphenylphosphine oxide. The complexes 1-6, were used to study their influence upon the catalytic peroxidation of the linoleic acid by the enzyme lipoxygenase (LOX) experimentally and theoretically. The binding of 1-4 with LOX was also investigated by saturation transfer difference H-1 NMR experiments (STD). (C) 2011 Elsevier B. V. All rights reserved.
Institution and School/Department of submitter: Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
Keywords: bioinorganic chemistry,copper(i) complexes,silver(i) complexes,crystal structures,photolysis,halide coordination-compounds,crystal-structure,molecular-structure,heterocyclic thiones,geometric preferences,disulfide complex,cu(i) complexes,triphenylphosphine,ligand,lipoxygenase
ISSN: 0020-1693
Link: <Go to ISI>://000300614000020
Publisher: Elsevier
Appears in Collections:Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά)

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