Copper Chalcogenide Clusters Stabilized with Ferrocene-Based Diphosphine Ligands
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- 作者：Chhatra B. Khadka ; Bahareh Khalili Najafabadi ; Mahdi Hesari ; Mark S. Workentin ; John F. Corrigan
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：June 17, 2013
- 年：2013
- 卷：52
- 期：12
- 页码：6798-6805
- 全文大小：485K
- 年卷期：v.52,no.12(June 17, 2013)
- ISSN：1520-510X
文摘
The redox-active diphosphine ligand 1,1鈥?bis(diphenylphosphino)ferrocene (dppf) has been used to stabilize the copper(I) chalcogenide clusters [Cu12(渭4-S)6(渭-dppf)4] (1), [Cu8(渭4-Se)4(渭-dppf)3] (2), [Cu4(渭4-Te)(渭4-畏2-Te2)(渭-dppf)2] (3), and [Cu12(渭5-Te)4(渭8-畏2-Te2)2(渭-dppf)4] (4), prepared by the reaction of the copper(I) acetate coordination complex (dppf)CuOAc (5) with 0.5 equiv of E(SiMe3)2 (E = S, Se, Te). Single-crystal X-ray analyses of complexes 1鈥?b>4 confirm the presence of {Cu2xEx} cores stabilized by dppf ligands on their surfaces, where the bidentate ligands adopt bridging coordination modes. The redox chemistry of cluster 1 was examined using cyclic voltammetry and compared to the electrochemistry of the free ligand dppf and the corresponding copper(I) acetate coordination complex 5. Cluster 1 shows the expected consecutive oxidations of the ferrocene moieties, CuI centers, and phosphine of the dppf ligand.