Binary α-Unsaturated Palladium Carboxylates and Their Complexes with Morpholine Derivatives: the Crystal Structure of Palladium Carbamoyl Crotonate (OC4H8NH)2Pd[OC4H8N(C=O)](MeCH=CHCO2) • H2O, a Product of the First Inner-Sphere Amination Reaction of α-Unsaturated Palladium Carbonyl Carboxylates with Morpholine

Binary alpha-unsaturated palladium carboxylates have been synthesized by substitution of alpha-unsaturated acids RCOOH (R is CH2=C(Me), MeCH=CH, PhCH=CH) for the acetate ion in Pd-3(mu-MeCOO)(6). These carboxylates react with amines A (A is morpholine (M), methylmorpholine (MM), or thiomorpholine (MS)) to give trans-Pd(A)(2)(RCOO)(2) similar to trans-A(2)(MeCO2)(2). The structures of the trans-Pd(A)(2)(RCOO)(2) complexes (R is MeCH=CH; A is M, MM, MS) have been determined by X-ray crystallography. The effect of solvent on the crystal structure of the complexes has been demonstrated for trans-(MeCH=CHCO2)(2)Pd(C4H9NO)(2) as an example. The amination reaction of palladium carbonyl crotonate with a secondary amine, morpholine, has been studied for the first time. The reaction involves disproportionation of Pd(I) into Pd(0) and Pd(II) and leads to the first unsaturated palladium(II) carbamoyl carboxylate-palladium carbamoyl crotonate trans-(OC4H8NH)(2)Pd[OC4H8NC(=O)](MeCH=CHCO2) center dot H2O, as well as to trans-M2Pd(MeCH=CHCO2)(2) and (C4H10NO)(+)(MeCH=CHCO2)(-). The structures of these compounds have been proved by X-ray crystallography.