Charmier M Adilia Januario, Haukka Matti, Pombeiro Armando J L
Centro de Quimica Estrutural, Instituto Superior Tecnico, Complexo I, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
Dalton Trans. 2004 Sep 7(17):2741-5. doi: 10.1039/B406191H. Epub 2004 Jul 28.
[PtCl2(RCN)2] (1a R=CH2CO2Me, 1b R=CH2Cl) prepared upon EtCN replacement at [PtCl2(EtCN)2] by the appropriate organonitrile, react with a cyclic nitrone -O-+N=CHCH2CH2C(Me)2, under mild conditions, to give, in an unprecedented single-pot synthesis involving spontaneous N-O bond cleavage, the ketoimino complexes trans-[PtCl2[RC(=O)N=CN(H)C(Me)2-CH2CH2]2 (2a, 2b) with two (pyrrolidin-2-ylidene)amino ligands. The analogous 2c (R=Et) and 2d (R=Ph) are formed by treatment with H2, in the absence of any added catalyst, of the Delta4-1,2,4-oxadiazoline complexes trans-[PtCl2[N=C(R)ONC(Me)2CH2CH2CH]2] (3a R=Et, 3b R=Ph) derived from the [2 + 3]-cycloaddition of the cyclic nitrone with the appropriate organonitrile complex of type 1. The compounds were characterized by elemental analyses, IR, 1H, (13C and 195Pt NMR spectroscopies, FAB mass spectrometry and X-ray structure analyses for 2a and 2d.
通过用适当的有机腈在[PtCl₂(EtCN)₂]中取代乙腈制备的[PtCl₂(RCN)₂]（1a，R = CH₂CO₂Me；1b，R = CH₂Cl），在温和条件下与环状硝酮-O⁺N=CHCH₂CH₂C(Me)₂反应，通过涉及自发N-O键断裂的前所未有的单锅合成，得到具有两个（吡咯烷-2-亚基）氨基配体的酮亚胺配合物反式-[PtCl₂[RC(=O)N=CN(H)C(Me)₂-CH₂CH₂]₂]（2a，2b）。类似的2c（R = Et）和2d（R = Ph）是通过在没有任何添加催化剂的情况下用H₂处理由环状硝酮与适当的1型有机腈配合物的[2 + 3]环加成衍生的Δ⁴-1,2,4-恶二唑啉配合物反式-[PtCl₂[N=C(R)ONC(Me)₂CH₂CH₂CH]₂]（3a，R = Et；3b，R = Ph）形成的。通过元素分析、红外光谱、¹H、¹³C和¹⁹⁵Pt核磁共振光谱、快原子轰击质谱以及对2a和2d的X射线结构分析对这些化合物进行了表征。
