Diruthenium Phenylacetylide Complexes Bearing para-/meta-Amino Phenyl Substituents

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• 作者：Steven P. Cummings ; Zhi Cao ; Carl W. Liskey ; Alex R. Geanes ; Phillip E. Fanwick ; Kerry M. Hassell ; Tong Ren
• 刊名：Organometallics
• 出版年：2010
• 出版时间：June 28, 2010
• 年：2010
• 卷：29
• 期：12
• 页码：2783-2788
• 全文大小：854K
• 年卷期：v.29,no.12(June 28, 2010)
• ISSN：1520-6041

文摘

Presented herein is the synthesis and characterization of four diruthenium(II,III) compounds of formulas Ru₂(Xap)₄(C≡C-C₆H₄-4-NH₂) (Xap is 2-anilinopyridinate, 1a; and 2-(3,5-dimethoxy)anilinopyridinate, 1b) and Ru₂(Xap)₄(C≡C-C₆H₄-3-NH₂) (2a/2b). X-ray structural studies of compounds 1b and 2a revealed minimal changes in the coordination sphere of the Ru₂ core. Voltammetric measurements showed that compounds 1 exhibit three one-electron redox processes: a reversible reduction of Ru₂, a reversible oxidation of Ru₂, and a quasi-reversible oxidation of an amino group. Compounds 2 display the same Ru₂-based redox processes but not the −NH₂ oxidation. Compounds 1a/1b were successfully converted to the corresponding diazonium salts [Ru₂(Xap)₄-(C≡C-C₆H₄-4-N₂)](BF₄) (3a/3b) via oxidation by nitrosonium tetrafluoroborate, which was generated in situ from t-BuONO and BF₃. However, the attempt to convert compounds 2 to the corresponding diazonium salts was unsuccessful. DFT calculations of model compounds were performed to rationalize some unusual structural and electrochemical characteristics observed for compounds 1/2.