title: Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles.
abstract: The metal-mediated iminoacylation reaction of ketoximes or aldoximes upon treatment with the organonitrile platinum(IV) complexes trans-[PtCl(4)(RCN)(2)] proceeds under relatively mild conditions in acetonitrile (R = Me) or in chloroform (R = CH(2)Ph, Ph) to give trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] (R(1) = R(2) = Me; R(1)R(2) = C(4)H(8), R(1)R(2) = C(5)H(10), R(1)R(2) = (H)Ph, R(1)R(2) = (H)C(6)H(4)(OH)-o; 1-14) in 90-95% yield. All these compounds were characterized by elemental analyses (C, H, N, Cl, Pt), FAB mass spectrometry, and IR and (1)H, (13)C{(1)H}, and (195)Pt NMR spectroscopies. X-ray structure determinations of [PtCl(4)(NH=C(Me)ON=CMe(2))(2)] (1) and [PtCl(4){NH=C(Me)ON=C(C(5)H(10))}(2)] (3) disclosed their overall trans-configuration and the amidine one-end rather than N,N-bidentate coordination mode of the N-donor ligands. The iminoacyl species are in E-conformation which is held by a rather weak N-H.N hydrogen bond between the amidine =NH atom and the oxime nitrogen with the following observed distances and angles for 1 and [3]: N(1).N(2), and N(1)-H, N(1)H.N(2) are 2.605 [2.592], 0.74 [0.71], and 2.20 [2.25] Å; N(1)-H.N(2) is 115 degrees [111 degrees ]. No evidence of the Z-conformation in solution was obtained by NMR spectroscopy. Compounds trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] are unexpectedly stable toward hydrolysis both in the solid state and in solutions.
authors.affiliation: Department of Chemistry, St. Petersburg State University, 198904 Stary Petergof, Russian Federation, Inorganic Chemistry, St. Petersburg State Technological Institute, Zagorodny Pr. 49, 198013 St. Petersburg, Russian Federation, and Complexo I, Instituto Supérior Técnico, Av. Rovisco Pais, 1096 Lisbon Codex, Portugal.
authors.forename: Vadim Yu.
authors.initials: VY
authors.lastname: Kukushkin
authors.forename: Tatyana B.
authors.initials: TB
authors.lastname: Pakhomova
authors.forename: Yuri N.
authors.initials: YN
authors.lastname: Kukushkin
authors.forename: Rudolf
authors.initials: R
authors.lastname: Herrmann
authors.forename: Gabriele
authors.initials: G
authors.lastname: Wagner
authors.forename: Armando J. L.
authors.initials: AJ
authors.lastname: Pombeiro