Filling a Gap: Electrochemical Property Comparison of the Completed Compound Series [Mo2(DArF)n(O2C-Fc)4–n] (DArF = N,N′-Diarylformamidinate; O2C-Fc = Ferrocenecarboxylate)

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• 作者：Xu-Min Cai ; Teresa K. Meister ; Alexander P?thig ; Fritz E. Kühn
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：January 19, 2016
• 年：2016
• 卷：55
• 期：2
• 页码：858-864
• 全文大小：397K
• ISSN：1520-510X

文摘

The reaction of cis-[Mo₂(O₂C-Fc)₂(NCCH₃)₄][BF₄]₂ (cis-1) with two electronically different N,N′-diarylformamidinate (DArF) ligands (DArF = N,N′-bis(p-trifluoromethylphenyl)formamidinate (DTfmpF), N,N′-bis(p-anisyl)formamidinate (DAniF)) results in the isolation of the tris- and monosubstituted complexes [Mo₂(DTfmpF)₃(O₂C-Fc)] (2a) and [Mo₂(DAniF)(O₂C-Fc)₃] (2b). These complexes complete the series of [Mo₂(DArF)_n(O₂C-Fc)_4–n] (n = 4–0) type compounds, thus allowing for a comprehensive study. On the basis of the oxidation potential E_1/2([Mo₂]p>4+p>/[Mo₂]p>5+p>) of all Mo₂ complexes, ligand basicity is found to decrease in the order DAniFp>–p> > DTfmpFp>–p> > Fc–CO₂p>–p> ? CH₃CN. In addition, no direct electronic interaction between the trans-positioned Fc units in complex 2b is detected, which is attributed to the full overlap of all Fc oxidation processes. Furthermore, the low-energy absorption bands of compounds 2a,b are located at different positions in their respective UV–vis spectra.