Autor: |
Kukushkin, Vadim Yu., Ilichev, Igor V., Zhdanova, Maria A., Wagner, Gabriele, Pombeiro, Armando J. L. |
Zdroj: |
Journal of the Chemical Society, Dalton Transactions; May 21, 2000, Vol. 2000 Issue: 10 p1567-1572, 6p |
Abstrakt: |
Reaction of the acetonitrile complex [RhCl3(MeCN)3] with 2-propanone oxime, Me2C&z.dbd6;NOH, or, alternatively, interaction of [RhCl3(Me2C&z.dbd6;NOH)3] and acetonitrile led to the formation of two rhodium(III) products that contain newly formed chelated iminoacyl ligands, i.e. [RhCl3{NH=C(Me)ON=CMe2}(HON=CMe2)] 1 and [RhCl2{NH=C(Me)ON=CMe2}2]Cl 2. Complex 1 can be transformed to 2 by further reaction with acetonitrile. Metathesis of 2 and Na[SbF6] in water gave [RhCl2{NH=C(Me)ON=CMe2}2][SbF6] 3 that was structurally characterized by single-crystal X-ray diffraction. In 0.1 M HCl, 2 is subject to a facile stepwise hydrolysis of the two usually stable oxime C&z.dbd6;N bonds giving [RhCl3{NH=C(Me)ON=CMe2}{NH=C(Me)ONH2}]Cl·H2O 4, as the monohydrolysed product, and ultimately furnished [RhCl2{NH=C(Me)ONH2}2]Cl 5 that was characterized by X-ray diffraction. The latter complex can be converted into 2 on prolonged refluxing in an acetoneethanol mixture. |
Databáze: |
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