Reactivity of polynuclear palladium carboxylate complexes towards acetonitrile: synthesis and X-ray study of Pd2(C6H4-o-C(=NH)CH3)2(CH3CO2)2 and Pd5(CH3C(=N)OC(=N)CH3)(NO)(NO2)x(RCO2)7-x.

Reactions of the polynuclear palladium carboxylate complexes (binary palladium carboxylates and palladium nitrosyl carboxylates) with acetonitrile in some common organic solvents are described. It was found that reaction of palladium acetate Pd(3)(µ-CH(3)CO(2))(6) with acetonitrile and benzene leads to the formation of a binuclear complex Pd(2)(C(6)H(4)-o-C(=NH)CH(3))(2)(CH(3)CO(2))(2) containing molecules of orthometallated 1-phenylethanimine formed as a result of C-C-coupling of acetonitrile and benzene. Nitrosyl carboxylate complexes Pd(4)(NO)(2)(RCO(2))(6) promote more complicated transformations of acetonitrile that leads to the formation of coordinated acetimidic anhydride, which was found in Pd(5)(CH(3)C(=N)OC(=N)CH(3))(NO)(NO(2))(x)(RCO(2))(7-x) clusters. Structures of all the complexes contained products of acetonitrile transformations and a new palladium nitrosyl carboxylate Pd(4)(NO)(2)(cyclo-C(6)H(11)CO(2))(6) was studied with XRD. Analysis of the structures allowed finding a "building block" of palladium nitrosyl carboxylate clusters, that is a 4-nuclear metal chain -Pd(µ-RCO(2))(2)Pd(µ-NO)(µ-RCO(2))Pd(µ-RCO(2))(2)Pd-.

Palladium ketonyl carboxylate complexes--potential models of polynuclear intermediates in olefin oxidation: formation and X-ray structure of Pd6(µ-Cl)(2+x)(µ-CF3CO2)4(µ,κ(2)-CH2C(O)CMe3)(6-x) (x = 0, 2).

Reactions of Pd(4)(NO)(4)(CF(3)CO(2))(4) with olefins were studied, this Pd-cluster was shown to promote the oxidation of olefins into ketones, which were found as ketonyl ligands in complex products of the reaction; 6-nuclear palladium clusters with carboxylate and ketonyl ligands Pd(6)(µ-Cl)(x)(µ-CF(3)CO(2))(4)(µ,κ(2)-CH(2)C(O)CMe(3))(6-x) were characterized by XRD analysis.