Platinum complexes alkali metal salts

Dithiophosphato metal complexes are usually prepared by metathesis of metal halides with alkali metal or ammonium salts. A convenient method uses the redox reaction of his th iophosphory 1 )d is ulfanes (RO)2(S)PSSP(S)(OR)2, with metal species in low oxidation states resulting in the insertion of the metal into the sulfur-sulfur bond.24 Recently it was used for the synthesis of long alkyl chain, liquid platinum(II) dithiophosphates25 and for the synthesis of Ru (CO)2[S2P(OPr%]2 from Ru3(CO)i2 with (Pr 0)2(S)PSSP(S)(0Pr,)2.26... 

Oxalo-niobates or niobo-oxalates correspond to the vanado-oxalates, and contain both oxalic acid and niobic add radicals in the complex anion. The only known series possesses the general formula 3R aO. Nb 205.6C203.a H20, where R stands for an alkali metal. The sodium, potassium and rubidium salts are prepared by fusing one molecular proportion of niobium pentoxide with three molecular proportions of the alkali carbonate in a platinum crucible. The aqueous extract of the melt jjs poured into hot oxalic add solution concentration and cooling, or addition of alcohol or acetone, then brings about precipitation of the complex salt. Comparison of the dectrical conductivity measurements of solutions of the alkali oxalo-niobates with those of the alkali hydrogen oxalates determined under the same conditions indicates that the oxalo-niobates are hydrolysed in aqueous solution, and that their anions contain a complex oxalo-niobic acid radical.6... 

Gmelin Handbook of Inorganic Chemistry, System No. 68, Platinum. Main Volume, (a) Part A in Sections 1-6, 1938-1951 (Platinum Metals, Occurrence, History, Preparation, Alloys) (b) Part B The Element in Sections 1-4,1939-1942, Physical and Electrochemical properties of Platinum (Chemical reactions of Pt in Section 4) (c) Part C The Compounds of Platinum. Section 1. Compounds with Noble Gases, H, O, N, Halogens, S, Se, Te, B, C,Si, P, As, Sb, Bi, 1939 (d) Section 2. Compounds with the alkali metals and ammonium, mainly the alkali metal platinum double salts, 1940 . (e) Section 3 Other Compounds, 1940 (f) Part D Complexes with Neutral ligands, 1957. Supplement Volume (g) Part A. Section 1. Technology of Platinum Metals. 1986 (h) Section 2. Isotopes, Atoms, Molecules and Clusters. 1989. 

It is not clear when dithiocarbamates were first prepared, but certainly they have been known for at least 150 years, since as early as 1850 Debus reported the synthesis of dithiocarbamic acids (1). The first synthesis of a transition metal dithiocarbamate complex is also unclear, however, in a seminal paper in 1907, Delepine (2) reported on the synthesis of a range of aliphatic dithiocarbamates and also the salts of di-iTo-butyldithiocarbamate with transition metals including chromium, molybdenum, iron, manganese, cobalt, nickel, copper, zinc, platinum, cadmium, mercury, silver, and gold. He also noted that while dithiocarbamate salts of the alkali and alkali earth elements were water soluble, those of the transition metals and also the p-block metals and lanthanides were precipitated from water, to give salts soluble in ether and chloroform, and even in some cases, in benzene and carbon disulfide. 

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