Syntheses and structural studies of heterobimetallic thiocarboxylate complexes containing zinc and copper

Anionic zinc(II) complexes, [Zn(SCOR)(3)] [R = th (1)] have been used for the synthesis of heterobimetallic complexes, [(PPh3) Cu(mu-SCOR)(3)Zn(PPh3)] [R = Ph (2) and th (3)]. All the three complexes have been characterized by FTIR, H-1 and C-13 NMR spectroscopy. The synthetic reactions involved phosphine migration from Cu(I) to Zn(II) in the cases of 2 and 3. Molecular structures of the complexes have been determined by single crystal X-ray diffraction and the structural features have been explained on the basis of NBO calculations. The Cu-Zn distance in these molecules are shorter than the sum of their covalent radii indicating the existence of a bond between the metals. Electronic spectral behavior of the complexes have been explained by TDDFT calculations. Luminescence properties of 3 has also been studied in solid state. (C) 2012 Elsevier B.V. All rights reserved.