The synthesis of water soluble tertiary phosphines is a subject of long-term continuing interest. This interest primarily lies in their use as ligands for reactions where it is desirable to have the

The complexes [Pd (µ-) (L-L) ] 22+ (L-L = dppe, dcpe) act as catalysts in aqueous THF solution for the addition of water to the carbon-carbon double bond of diethyl maleate to give the alcohol, diethyl malate. This addition reaction of diethyl maleate to give diethyl malate, as well as its oxidation to diethyl oxaloacetate, is catalyzed in aqueous THF solution by a mixture of PdCU2-and CuCl2. Isomerization of diethyl maleate to diethyl fumarate, along with hydrolysis products of each alkene, is also observed with both catalyst systems. Mechanisms for these palladium(II) catalyzed reactions involving the protonolysis of an intermediate alkylpalladium complex are proposed. In aqueous solution, tertiary phosphines catalyze the cis-trans isomerization of diethyl maleate to diethyl fumarate.

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Two series of µ-hydroxy-bridged complexes, [ (µ-) 2]2( 4)2 and [ (µ-)( -)] 2(BF4)2, have been prepared by treating PdCl2L2 (L = PPh3, PPh2Me) and PdCl2(L-L) (L-L = Ph2PCH2CH2PPh2(dppe), Cy2PCH2CH2PCy2-(dcpe)) with silver tetrafluoroborate in aqueous acetone solvent. These µ-hydroxy complexes react with carbon dioxide in aqueous acetone to give the bis(bicarbonato) complexes Pd(0C(0)0H)2L2 and Pd(OC(0)OH)2(L-L). Pd(0C(0)0H)2dppe crystallizes in the monoclinic space group, Cc (No. 9), with a = 10.410 (1) Á, b = 15.703 (2) Á, c = 16.365 (2) A, ß = 100.22 (1)°, V = 2633 (2) A3 and Z = 4. The structure was refined with 3130 unique and 2730 observed (/ > 3 ( )) data to give R = 0.021 and Rw = 0.028.

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