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

• Published in: Russian journal of inorganic chemistry 2015-07, Vol.60 (7), p.848-860
• Main Authors: Efimenko, I. A., Ankudinova, P. V., Kuz’mina, L. G., Churakov, A. V., Ivanova, N. A., Demina, L. I., Erofeeva, O. S.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Inorganic Chemistry; XXVI International Chugaev Conference on Coordination Chemistry
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023615070050

Binary α-unsaturated palladium carboxylates have been synthesized by substitution of α-unsaturated 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 crystallography. 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 disproportionation of Pd(I) into Pd(0) and Pd(II) and leads to the first unsaturated palladium(II) carbamoyl carboxylate—palladium 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.