Experimental and theoretical studies of palladium(II) and platinum(II) complexes derived from di-(2-pyridyl)methyl-N,N′-dibenzyldithiocarbamate

• Published in: Polyhedron 2019-04, Vol.162, p.177-185
• Main Authors: Andrade-López, Noemí, González-Montiel, Simplicio, Ramos-Espinosa, Ángel, Camacho-Mendoza, Rosa L., Vásquez-Pérez, José Manuel, Sánchez-Cabrera, Gloria, Zuno-Cruz, Francisco Javier
• Format: Article
• Language: English
• Subjects: DFT calculations; Dipyridyl complexes; NMR; PdII and PtII complexes; X-ray diffraction
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2019.01.059

The synthesis and characterization of three complexes of PdII and PtII derivatives of di-(2-pyridyl)methyl-N,N′-dibenzyldithiocarbamate (L) of formula [MII(L)Cl2], M = Pd (1); M = Pt, (2), and [PdII(L)2](BF4)2 (3) is described. Molecular structures of complexes 1–3 by X-ray diffraction studies displayed a κ2N coordination mode of L toward the metallic centers. The N,N′-dibenzyldithiocarbamate group is located in a flagpole position, enhancing the formation of intramolecular M⋯S interactions in solid state. The nature of the M⋯S and CH⋯S interactions in complexes 1–3 was analyzed by means of density functional methods. [Display omitted] Di-(2-pyridyl)methyl-N,N′-dibenzyldithiocarbamate (L) and their metal complexes of formula [MII(L)Cl2], M = Pd (1); M = Pt, (2), and [PdII(L)2](BF4)2 (3) were synthesized and characterized in solution and in solid state by NMR, elemental analysis and vibrational spectroscopy, respectively. The crystal structures of the 1, 2, and 3 were stablished by X-ray single crystal diffraction. In all complexes, the molecular structures displayed the formation of six-membered chelate rings with a square planar local geometry around the MII cations. The N,N′-dibenzyldithiocarbamate group is located in a flagpole position, enhancing the formation of intramolecular M⋯S interactions in solid state. The nature of the M⋯S and CH⋯S interactions in complexes 1–3 was analyzed by means of density functional methods.