The interaction of palladium(I1) nitrate with acetic and propionic acids produces the brown carboxylates Pd(OCOR)2 ; the benzoate, trifluoroacetate, and pentafluoropropionate are obtained via exchange reactions. Although the fluoro-carboxylates are monomeric, the other compounds are trimers in solution a t 37".The interaction of the carboxylates with various amines, triphenylphosphine and triphenylarsine gives complexes of the type trans-[Pd (OCOR) 2L2) with unidentate carboxylate groups. Diacetatoplatinum(11) was obtained by the reduction of an acetic acid solution of hexahydroxyplatinate(1v) with formic acid. It is trimeric, not isomorphous with [Pd(OCOMe)2),, and does not undergo cleavage reactions with donor ligands. Studies on rhodium(I1) carboxylates have been confirmed and extended. Palladhim CarboxyZates.-Diacetatopalladium(I1) can be obtained as brown crystals from the interaction of slightly acid solutions of palladium(11) nitrate with glacial acetic acid, or by dissolving palladium sponge suspended in hot glacial acetic acid, by the addition of the minimum quantity of nitric acid. The propionate can be made directly in the same way, while the benzoate, trifluoroacetate, and pentafluoropropionate can be obtained from the acetate by exchange reactions.

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The interaction of triphenylphosphine with methanolic solutions of commercial hydrated ruthenium trichloridet leads to mononuclear compleses [RUC~~{P(C&%)~) 41 and [RuC121 P(C&ts)3} s ] , the product depending upon the reaction conditions.1 However, similar reactions, involving mixed alkyl aryl tertiary phosphines, yield binuclear compleses of the type [ R U~C~~( P R~)~] C~ [R = (C2H 5) 2 (CeH d, (C2H d (CsHs) 2, etC.1. * supply "ruthenium trichloride trihydrate" with ca. 44.6% Ru; other suppliers' products are similar. These materials are mainly ruthenium(1V) complexes. On repeated evaporation almost to dryness with concentrated hydrochloric acid, a solution containing the ruthenium (111) complex ion R u C l P is obtained. For the present purpose, the commercial material may be used; identical complexes are obtained by using the Ru(II1) solutions, however.

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