Synthesis and Structural Analysis of New Palladium(II) Thiosaccharinates with Triphenylphosphane or Diphosphanes |
| |
| Authors: | Susana H Tarulli Oscar V Quinzani Prof Dr Sandra D Mandolesi Jorge A Guida Gustavo A Echeverría Oscar E Piro Eduardo E Castellano |
| |
| Institution: | 1. INQUISUR, Departamento de Química, Universidad Nacional del Sur, Avda. Alem 1253, B8000CPB, Bahía Blanca, Argentina;2. CEQUINOR, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C.C. 962, 1900 La Plata, Argentina, and Departamento de Ciencias Básicas, Universidad Nacional de Luján, Rutas 5 y 7, Luján, Argentina;3. Departamento de Física and Instituto IFLP, (Conicet, CCT La Plata), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C.C. 67, 1900 La Plata, Argentina;4. Instituto de Física de São Carlos, Universidade de São Paulo, CP. 369, 13560 São Carlos (SP), Brazil |
| |
| Abstract: | A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh3), bis(diphenylphosphanyl)methane (dppm), and bis(diphenylphosphanyl)ethane (dppe) have been prepared and characterized. From mixtures of thiosaccharin, Htsac, and palladium(II) acetylacetonate, Pd(acac)2, the palladium(II) thiosaccharinate, Pd(tsac)2 (tsac: thiosaccharinate anion) ( 1 ) was prepared. The reaction of 1 with PPh3, dppm, and dppe leads to the mononuclear species Pd(tsac)2(PPh3)2 · MeCN ( 2 ), Pd(tsac)2(dppm)] ( 3 ), Pd(tsac)2(dppm)2 ( 4 ), and Pd(tsac)2(dppe)] · MeCN ( 5 ). Compounds 2 , 4 , and 5 have been prepared also by the reaction of Pd(acac)2 with the corresponding phosphane and Htsac. All the new complexes have been characterized by chemical analysis, UV/Vis, IR, and Raman spectroscopy. Some of them have been also characterized by NMR spectroscopy. The crystalline structures of complexes 3 , and 5 have been studied by X‐ray diffraction techniques. Complex 3 crystallizes in the monoclinic space group P21/n with a = 16.3537(2), b = 13.3981(3), c = 35.2277(7) Å, β = 91.284(1)°, and Z = 8 molecules per unit cell, and complex 5 in P21/n with a = 10.6445(8), b = 26.412(3), c = 15.781(2) Å, β = 107.996(7)°, and Z = 4. In compounds 3 and 5 , the palladium ions are in a distorted square planar environment. They are closely related, having two sulfur atoms of two thiosaccharinate anions, and two phosphorus atoms of one molecule of dppm or dppe, respectively, bonded to the PdII atom. The molecular structure of complex 3 is the first reported for a mononuclear PdII‐dppm‐thionate system. |
| |
| Keywords: | Palladium Thiosaccharin Diphosphanes X‐ray diffraction Coordination chemistry |
|
|
