Lasri Jamal, Charmier M Adília Januário, Guedes da Silva M Fátima C, Pombeiro Armando J L
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
Dalton Trans. 2006 Nov 14(42):5062-7. doi: 10.1039/b611341a. Epub 2006 Sep 11.
The metal-mediated iminoacylation of ketoximes R1R2C=NOH (1a R1 = R2 = Me; 1b R1 = Me, R2 = Et; 1c R1R2 = C4H8; 1d R1R2 = C5H10) upon treatment with the platinum(II) complex trans-[PtCl2(NCCH2CO2Me)2] 2a with an organonitrile bearing an acceptor group proceeds under mild conditions in dry CH2Cl2 to give the trans-[PtCl2{NH=C(CH2CO2Me)ON=CR1R2}2] 3a-d isomers in moderate yield. The reaction of those ketoximes with trans-[PtCl2(NCCH2Cl)2] 2b under the same experimental conditions gives a 1 : 1 mixture of the isomers trans/cis-[PtCl2{NH=C(CH2Cl)ON=CR1R2}2] 3e-h and 4e-h in moderate to good yield. These reactions are greatly accelerated by microwave irradiation to give, with higher yields (ca. 75%), the same products which were characterized by IR and 1H, 13C and 195Pt NMR spectroscopies, FAB-MS, elemental analysis for the stable trans isomers, and X-ray diffraction analysis (3f). The diiminoester ligand in 3a was liberated upon reaction of the complex with a diphosphine.
用带有受体基团的有机腈处理酮肟R1R2C=NOH（1a：R1 = R2 = 甲基；1b：R1 = 甲基，R2 = 乙基；1c：R1R2 = C4H8；1d：R1R2 = C5H10），与铂（II）配合物反式-[PtCl2(NCCH2CO2Me)2] 2a在温和条件下于干燥的二氯甲烷中反应，以中等产率得到反式-[PtCl2{NH=C(CH2CO2Me)ON=CR1R2}2] 3a - d异构体。在相同实验条件下，那些酮肟与反式-[PtCl2(NCCH2Cl)2] 2b反应，以中等至良好产率得到反式/顺式-[PtCl2{NH=C(CH2Cl)ON=CR1R2}2] 3e - h和4e - h异构体的1 : 1混合物。这些反应通过微波辐射大大加速，以更高产率（约75%）得到相同产物，通过红外光谱、1H、13C和195Pt核磁共振光谱、快原子轰击质谱、对稳定反式异构体的元素分析以及X射线衍射分析（3f）对产物进行了表征。配合物与二膦反应时，3a中的二亚氨基酯配体被释放出来。
