The first example of ligand-mediated dehydration of aldoximes

Abstract The nitrile complex trans -[PtCl 4 (EtCN) 2 ] reacts with the aldoximes HONC(H)R [R=C(Ph)(O), Me, Ph] in CH 2 Cl 2 to afford products of the addition of the aldoxime HON group across the nitrile CN triple bond, i.e. trans -[PtCl 4 {NHC(Et)ONC(H)R} 2 ] ( 1 – 3 ). These compounds were characterized by elemental analyses, FAB MS, IR and 1 H and 13 C{ 1 H} spectroscopies and X-ray structure determination has been performed for 1 . In CHCl 3 solution, 1 – 3 undergo the spontaneous imine ligand splitting to achieve the carboxamide complex trans -[PtCl 4 {NHC(Et)OH} 2 ] and RCN thus giving the first example of a ligand-mediated dehydration of aldoximes. The carboxamide and RCN products are also formed upon treatment of trans -[PtCl 4 (EtCN) 2 ] with 2 equiv. of HONC(H)R in CH 2 Cl 2 .