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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Tetrakis(ferrocenecarbonitrile) copper(I) complexes
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Tetrakis(ferrocenecarbonitrile) copper(I) complexes

机译：四（二茂铁腈）铜（I）络合物

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摘要

The homoleptic tetrakis(ferrocenecarbonitrile) copper(I) complexes [Cu(N≡CFc)_4]A [A = BF_4 (3a), A = SO _3CF_3 (3b)] were succefully prepared by treatment of copper with the copper(II) salt [CuA_2]·xH_2O [A = BF _4, x = 5 (1a); A = SO_3CF_3, x = 0 (1b)] in presence of cyanoferrocene (2). For 3a the tetrahedral arrangement of the four ferrocenecarbonitrile ligands at the copper atom was proven by single X-ray diffraction studies. The FcC≡N units are weakly bonded to copper, which is reflected by a complete ligand exchange upon addition of MeC≡N forming [Cu(N≡CMe)_4]BF_4 (4). Electrochemical measurements of 3a revealed that all four ferrocenyl units are oxidized in a close potential range and the individual processes are not resolved in the cylic voltammogram. Due to the decrease of electron density at the ferrocenyl termini, the redox event is merely shifted to 456 mV (for comparison, free 2 has E°′ = 436 mV). For 3a intervalence charge transfer (IVCT) absorption between Fe ~(II)/Fe~(III) and/or Cu~I/Fe~(III) could not be observed in the in situ UV/Vis/NIR spectra in any oxidation state. This alluded that no electronic interaction between the Fc/Fc~+ termini over the -C≡N-Cu~I-N≡C- connectivities takes place. Nevertheless, upon oxidation a ligand-to-metal charge transfer (LMCT) band of the ferrocenium groups at 643 nm is visuable accompanied with a shift in the d-d transition absorptions of the central iron atoms.
机译：通过用铜（II）处理铜，成功制备了均化的四（二茂铁腈）铜（I）配合物[Cu（N≡CFc）_4] A [A = BF_4（3a），A = SO _3CF_3（3b）]。盐[CuA_2]·xH_2O [A = BF _4，x = 5（1a）;在氰基二茂铁（2）存在下，A ＝ SO_3CF_3，x ＝ 0（1b）。对于3a，通过单X射线衍射研究证明了在铜原子上的四个二茂铁甲腈配体的四面体排列。 FcC≡N单元与铜弱结合，这通过添加MeC≡N形成[Cu（N≡CMe）_4] BF_4（4）时完全的配体交换来反映。 3a的电化学测量表明，所有四个二茂铁基单元均在近电势范围内被氧化，单个过程在循环伏安图中未解决。由于二茂铁基末端的电子密度降低，氧化还原事件仅移至456 mV（为进行比较，游离2的E°'= 436 mV）。对于3a间隔的Fe〜（II）/ Fe〜（III）和/或Cu〜I / Fe〜（III）之间的电荷转移（IVCT）吸收在任何氧化中均未在原位UV / Vis / NIR光谱中观察到州。这暗示在Fc-Fc- +末端之间在-C≡N-Cu-I-N≡C-连接性上没有发生电子相互作用。然而，在氧化时，在643nm处可见二茂铁基团的配体-金属电荷转移（LMCT）带，并且伴随着中心铁原子的d-d跃迁吸收的移动。

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