Kukushkin Vadim Yu., Pakhomova Tatyana B., Kukushkin Yuri N., Herrmann Rudolf, Wagner Gabriele, Pombeiro Armando J. L.
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.
Inorg Chem. 1998 Dec 14;37(25):6511-6517. doi: 10.1021/ic9807745.
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.
酮肟或醛肟与有机腈铂（IV）配合物反式-[PtCl₄(RCN)₂] 进行金属介导的亚氨基酰化反应，该反应在乙腈（R = Me）或氯仿（R = CH₂Ph、Ph）中相对温和的条件下进行，生成反式-[PtCl₄(NH=C(R)ON=CR₁R₂)₂]（R₁ = R₂ = Me；R₁R₂ = C₄H₈、R₁R₂ = C₅H₁₀、R₁R₂ = (H)Ph、R₁R₂ = (H)C₆H₄(OH)-o；1 - 14），产率为90 - 95%。所有这些化合物均通过元素分析（C、H、N、Cl、Pt）、快原子轰击质谱以及红外光谱、¹H、¹³C{¹H}和¹⁹⁵Pt核磁共振光谱进行了表征。[PtCl₄(NH=C(Me)ON=CMe₂)₂]（1）和[PtCl₄{NH=C(Me)ON=C(C₅H₁₀)}₂]（3）的X射线结构测定揭示了它们整体的反式构型以及脒基一端而非N,N - 双齿配位模式的氮供体配体。亚氨基酰物种呈E - 构象，通过脒基 =NH原子与肟氮之间相当弱的N - H···N氢键保持，对于1和[3]观察到的距离和角度如下：N(1)···N(2)以及N(1) - H、N(1)H···N(2)分别为2.605 [2.592] Å、0.74 [0.71] Å和2.20 [2.25] Å；N(1) - H···N(2)为115° [111°]。通过核磁共振光谱未获得溶液中Z - 构象的证据。反式-[PtCl₄(NH=C(R)ON=CR₁R₂)₂]化合物在固态和溶液中对水解均出乎意料地稳定。
