N-cyanoacetylurethane complexes of palladium(II), and the x-ray crystal structure of trans-[PdCl{EtO 2C NC(O)CH 2CN}(PPh 3) 2

Abstract

Reaction of [PdCl 2(DPPE)] (DPPE = Ph 2PCH 2CH 2PPh 2) with N-cyanoacetylurethane, NCCH 2NHCO 2Et, and silver(I) oxide gave the four-membered ring palladalactam complex [P d{CH(CN)C(O)N (CO 2Et)}(DPPE)] in high yield. In contrast, reaction of [PdCl 2(PPh 3) 2] with N-cyanoacetylurethane and silver(I) oxide gave the monodentate amide complex trans-[PdCl{EtO 2C NC(O)CH 2CN}(PPh 3) 2] in high yield. The amide complex was characterized by multinuclear NMR spectroscopy and by a single-crystal X-ray diffraction study. The plane of the N-bonded cyanoacetylurethane ligand is virtually perpendicular to the square-plane of the palladium coordination sphere.