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

Abstract

Binary α unsaturated palladium carboxylates have been synthesized by substitution of α unsatur ated acids RCOOH (R is CH 2 =C(Me), MeCH=CH, PhCH=CH) for the acetate ion in Pd 3 (μ 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 (MeCO 2 ) 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 crystallog raphy. The effect of solvent on the crystal structure of the complexes has been demonstrated for trans (MeCH=CHCO 2 ) 2 Pd(C 4 H 9 NO) 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 disproportion ation of Pd(I) into Pd(0) and Pd(II) and leads to the first unsaturated palladium(II) carbamoyl carboxylatepalladium carbamoyl crotonate trans (OC 4 H 8 NH) 2 Pd[OC 4 H8NC(=O)](MeCH=CHCO 2 ) ⋅ H 2 O, as well as to trans M 2 Pd(MeCH=CHCO 2 ) 2 and (C 4 H 10 NO) + (MeCH=CHCO 2 ) -. The structures of these compounds have been proved by X ray crystallography.