CONICET | Buscador de Institutos y Recursos Humanos

A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh3), bis(diphenylphosphino)methane (dppm), and bis(diphenylphosphino)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, UVvisible, 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 P21/n space group with a=16.3537(2), b=13.3981(3), c=35.2277(7) Å, beta=91.284(1)°, and Z=8 molecules per unit cell, and 5 in P21/n with a=10.6445(8), b=26.412(3), c=15.781(2) Å,beta=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 S-atoms of two thiosaccharinate anions, and two P-atoms of one molecule of dppm or dppe, respectively, bonded to the Pd(II) atom. The molecular structure of complex 3 is the first reported for a mononuclear Pd(II)-dppm-thionate system.3), bis(diphenylphosphino)methane (dppm), and bis(diphenylphosphino)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, UVvisible, 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 P21/n space group with a=16.3537(2), b=13.3981(3), c=35.2277(7) Å, beta=91.284(1)°, and Z=8 molecules per unit cell, and 5 in P21/n with a=10.6445(8), b=26.412(3), c=15.781(2) Å,beta=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 S-atoms of two thiosaccharinate anions, and two P-atoms of one molecule of dppm or dppe, respectively, bonded to the Pd(II) atom. The molecular structure of complex 3 is the first reported for a mononuclear Pd(II)-dppm-thionate system.