Low-valence triruthenium compounds via substitution of a bridging acetate in the parent Ru3O(OAc)(6) cluster core by 2,2 '-azobispyridine (abpy) or 2,2 '-azobis(5-chloropyrimidine) (abcp)
文献类型：期刊论文
| 作者 | H. Y. Ye ; F. R. Dai ; L. Y. Zhang ; Z. N. Chen |
| 刊名 | Inorganic Chemistry
 |
| 出版日期 | 2007-07 |
| 卷号 | 46期号:15页码:6129-6135 |
| 关键词 | intramolecular electron-transfer trinuclear ruthenium complex n-heterocyclic ligands vibrational time-scale redox behavior structural-characterization electrochemical properties reversible multistep isocyanide ligands state |
| ISSN号 | 0020-1669 |
| 中文摘要 | Reaction of oxo-centered Ru-3(III,III,III) precursor [Ru3O(OAc)(6)(py)(2)(CH3OH)](PF6) (1) with 1 equiv of 2,2'-azobispyridine (abpy) or 2,2'-azobis(5-chloropyrimidine) (abcp) induced the formation of stable Ru-3(III,III,II) derivatives [Ru3O(OAc)(5){mu-eta(1)(N),eta(2)(N,N)-L}(py)(2)](PF6) (L = abpy (2), abcp (3)). As established in the structure of 3 by X-ray crystallography, 2 or 3 is derived from 1 by substitution of the axial methanol and one of the bridging acetates in the parent Ru3O(OAc)(6) cluster core with abpy or abcp in an mu-eta(1)(N),eta(2)(N,N) bonding mode. Reduction of 3 by hydrazine induces isolation of one-electron reduced neutral Ru-3(III,II,II) product Ru3O(OAc)(5){mu-eta(1)(N),eta(2)(N,N)-abcp}(py)(2) (3a). As revealed by electrochemical and spectroscopic studies, substituting one of the bridging acetates in the parent Ru3O(OAc)(6) cluster core by abcp or abpy modifies dramatically the electronic and redox characteristics in the triruthenium derivatives. Relative to that for the parent compound [Ru3O(OAc)(6)(py)(3)](PF6) (E-1/2 = -0.46 V), triruthenium-based redox potential in the redox process Ru3OIII,III,III/Ru3OIII,III,II is significantly anodic-shifted to E-1/2 = +0.36 V for 2 and E-1/2 = +0.53 V for 3. Furthermore, the anodic shifts of redox potentials are progressively enhanced with a decrease of the formal oxidation states in the triruthenium cluster cores. As a consequence of remarkable positive shifts for redox potentials, the low-valence Ru-3(III,III,II) and Ru-3(III,II,II) species are stabilized and accessible. |
| 语种 | 英语 |
| 公开日期 | 2013-04-01 |
| 源URL | [http://ir.fjirsm.ac.cn/handle/350002/6819]  |
| 专题 | 福建物质结构研究所_中科院福建物质结构研究所_期刊论文 |
| 推荐引用方式 GB/T 7714 | H. Y. Ye,F. R. Dai,L. Y. Zhang,et al. Low-valence triruthenium compounds via substitution of a bridging acetate in the parent Ru3O(OAc)(6) cluster core by 2,2 '-azobispyridine (abpy) or 2,2 '-azobis(5-chloropyrimidine) (abcp)[J]. Inorganic Chemistry,2007,46(15):6129-6135. |
| APA | H. Y. Ye,F. R. Dai,L. Y. Zhang,&Z. N. Chen.(2007).Low-valence triruthenium compounds via substitution of a bridging acetate in the parent Ru3O(OAc)(6) cluster core by 2,2 '-azobispyridine (abpy) or 2,2 '-azobis(5-chloropyrimidine) (abcp).Inorganic Chemistry,46(15),6129-6135. |
| MLA | H. Y. Ye,et al."Low-valence triruthenium compounds via substitution of a bridging acetate in the parent Ru3O(OAc)(6) cluster core by 2,2 '-azobispyridine (abpy) or 2,2 '-azobis(5-chloropyrimidine) (abcp)".Inorganic Chemistry 46.15(2007):6129-6135. |
入库方式： OAI收割
来源：福建物质结构研究所
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