Preparation Of Transition Metal Complexes Of Phosphorothioate And Organic Acid, Structure And Performance

(1) Reaction of 2, 4-bis(4-methoxyphenyl) -1,3,2,4- dithiadiphosphetane-2, 4- disulfic (Lawesson's Reagent or LR, see Scheme 1) with o-phenylene diamine to give compound 1 as the product. While the methanol solution of compound 1 with the presence of NiCl2 gave its ring-cleavage product compound 2. The structures of both of them were characterized by single-crystal X-ray diffraction. The IR spectra also testify the structure detection.(2) The reaction of 2, 4-bis(4-methoxyphenyl)-l, 3, 2, 4- dithiadiphosphetane-2, 4-disulfide with NiCl2 or Co(CH3COO)2 in methanol or ethanol give novel sulfur-rich complexes: C16H20NiO4P2S4 (1), C18H24NiO4P2S4 (2) and C24H30CoO6P3S6 (4), respectively. With the presence of ethylenediamine at same condition complex C24H48N6NiO4P2S4 (3) is also achieved. These four novel sulfur-rich complexes were characterized by IR and X-ray crystallography, which indicate that the solvent can influence the crystal structure of complexes in the reaction between LR and metal salts.(3) Potassium-sodium tartrate reacts with CuCl2 to form heteronuclear tartrate complex C12H20Cu2KNaO24. It belongs to monoclinic system, P2(l) space group. The crystallographic data are: a =7.6429(15)A, b =20.753(4) A, c= 8.1058(16)A, a =90, 3 =112.06(3), r =90. Its X-ray crystal structure shows that two different coordination mode Cu(II) ions and two tartrate ligands consist a cycle. The cycles are connected by Na(I)-K(I) pairs and then form the complicate crystal structure through the hydrogen-bond network..(4) Two copper(II) sodium(I) coordination compounds of formula [C16H12CuNa2O10] (6) and [C6H8CuNa2O10] (7) were prepared and their structures were characterized by single-crystal X-ray diffraction, IR spectra and thermal analyses.