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New Zn(II) complexes with N2S2 Schiff base ligands. Experimental and theoretical studies of the role of Zn(II) in disulfide thiolate-exchange

  • Author(s): Amirnasr, M
  • Bagheri, M
  • Farrokhpour, H
  • Schenk, KJ
  • Mereiter, K
  • Ford, PC
  • et al.
Abstract

Described are the synthesis and characterization of two, potentially tetradentate, N S Schiff-base ligands, containing a disulfide bond, N,N′-bis(3-phenylprop-2-en-1-ylidene)-2,2′- disulfanediyldianiline (L ) and N,N′-bis(3,3-diphenylprop-2-en- 1-ylidene)-2,2′-disulfanediyldianiline (L ), and their reaction with Zn . Surprisingly, both L and L undergo reductive disulfide bond scission upon reaction with Zn in alcoholic media to give, under alcohol oxidation, the respective Zn(NS) complexes Zn(L ) (1) and Zn(L ) (2), where the L and L are the respective bidentate thiolate-imine anions. The ligands L and L and the complexes 1 and 2 have been characterized spectroscopically, and the crystal and molecular structures of the two complexes have been determined by single crystal X-ray diffraction. The coordination geometry around Zn(II) centers in both complexes is a distorted tetrahedron. In addition, DFT calculations (B3LYP/LANL2DZ/6-311++G(d,p)) support the structure of 1. Cyclic voltammetric studies demonstrate that Zn(II) shifts the reduction potential of the disulfide ligands L and L to less negative values thus making them more susceptible to reductive cleavage of the disulfide bond. The results of semi-empirical PM6 calculations offer key insight into the nature of the transition state for this reaction. © 2014 Elsevier Ltd. All rights reserved. 2 2 2 2 2 1 2 2+ 1 2 2+ 3 4 3 4 1 2 1 2

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