| Автор | Kaminskaia, Natalia V. |
| Автор | KostiÄ , Nenad M. |
| Дата выпуска | 2001 |
| dc.description | Several new palladium(II) complexes containing acetoxime as a unidentate ligand were synthesized from cis-[Pd(en)(solv)2]<sup>2+</sup> 1a and cis-[Pd(dtod)(solv)2]<sup>2+</sup> 1b, in which the displaceable ligand solv is water or acetone, en is ethane-1,2-diamine, and dtod is 3,6-dithia-1,8-octanediol. The acetoxime complexes are characterized by UV-visible spectrophotometry and <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy in solution. Acetoxime in the mono-oxime complexes cis-[Pd(en){N(OH)C(CH3)2}(solv)]<sup>2+</sup> 2a and cis-[Pd(dtod){N(OH)C(CH3)2}(solv)]<sup>2+</sup> 2b undergoes hydrolysis to acetone and hydroxylamine. The proposed mechanism involves internal attack of a Pd<sup>II</sup>-bound hydroxo ligand at the coordinated acetoxime. This palladium(II)-catalysed hydrolysis is at least 10<sup>4</sup> times faster than hydrolysis in the absence of a catalyst. The rate enhancement arises from polarization of acetoxime upon coordination to palladium(II), the availability of the nucleophilic hydroxo ligand, and close proximity of these two species. The complex [Pd(dien){N(OH)C(CH3)2}]<sup>2+</sup>, which contains the tridentate diethylenetriamine ligand, is almost unreactive toward hydrolysis because it lacks a Pd<sup>II</sup>-bound aqua or hydroxo ligand, so that the reaction occurs via the less-favorable external attack of solvent water. Acetoxime in the bis-acetoxime complex cis-[Pd(dtod){N(OH)C(CH3)2}2]<sup>2+</sup> 3b hydrolyses very slowly because this complex also lacks aqua or hydroxo ligands. Therefore, this complex was crystallized and its structure determined by X-ray crystallography. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Acetoxime coordinates to palladium(II) and is catalytically hydrolysed to acetoneâ Electronic supplementary information (ESI) available: diagrams of the palladium(II) and platinum(II) catalysts. See http://www.rsc.org/suppdata/dt/b0/b008753j/ |
| Тип | ART |
| Журнал | Dalton Transactions |
| Первая страница | 1083 |
| Последняя страница | 1086 |
| Аффилиация | Kaminskaia Natalia V.; Department of Chemistry, Iowa State University |
| Аффилиация | KostiÄ Nenad M.; Department of Chemistry, Iowa State University |
| Выпуск | 7 |
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