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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Intramolecular electronic communication in ferrocene-based β-diketonato copper(II) complexes as observed by an electrochemical study
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Intramolecular electronic communication in ferrocene-based β-diketonato copper(II) complexes as observed by an electrochemical study

机译：电化学研究观察到二茂铁基β-二酮铜（II）配合物中的分子内电子通讯

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摘要

The reaction of [Cu(OAc)_2.H_2O]_2 (1) with β-diketones FcCOCH_2COR (R = CF_3, 2a, CH_3, 2b, Ph = C_6H_5, 2c, and Fc = Fe(η~5-C _5H_4)(η~5-C_5H_5), 2d), afforded in a straightforward synthetic methodology a series of ferrocenyl-functionalized β-diketonato copper(II) complexes 3a-3d of general formula [Cu(FcCOCHCOR)_2]. The environment around copper(II) is square planar with the ferrocenyl moieties being positioned opposite to each other. All complexes display in their cyclic voltammograms resolved and electrochemical reversible ferrocenyl oxidations in the range 98 ≤ E ~o′ ≤ 420 mV versus FcH/FcH~+. An electrochemical and chemical irreversible Cu(II) reduction was observed in the range -1624 ≤ E_(pc) ≤ -1102 mV. Good intramolecular communication between neutral ferrocenyl and oxidised, positively charged ferrocenium cations explained the well resolved ferrocenyl redox processes. The observed intramolecular communication was quantified with the linear equation E~o′ = 98.5Σ_χ_R - 629 which relates formal ferrocenyl oxidation potentials with the sum of R-group electronegativities, Σ_χ _R. It was possible to show that in [Cu(FcCOCHCOFc)_2], 3d, one ferrocenyl group on each β-diketonato ligand is first oxidized before the second ferrocenyl group on the same β-diketonato ligand is oxidized. In a spectro-electrochemical study, an intervalent charge transfer band (IVCT) could be detected for the mixed valent intermediates of 3d that are electrochemically generated. For complex 3a, only the normal ligand to metal charge transfer band at ca. 650 nm was observed. This demonstrate that communication between Fc and Fc~+ groups are more effective within a specific β-diketonato ligand, such as (Fc~+COCHCOFc) in 3d, than across a copper centre, [Fc~+COCHCOR)Cu(FcCOCHCOR)], presumably because of the longer distance between the Fc?Fc~+ species across the copper centre than within a single ligand.
机译：[Cu（OAc）_2.H_2O] _2（1）与β-二酮FcCOCH_2COR（R = CF_3，2a，CH_3，2b，Ph = C_6H_5，2c，Fc = Fe（η〜5-C _5H_4） （η〜5-C_5H_5），2d），通过直接合成方法获得了一系列具有通式[Cu（FcCOCHCOR）_2]的二茂铁基官能化的β-二酮铜（II）配合物3a-3d。铜（II）周围的环境呈方形平面，二茂铁基部分彼此相对放置。所有复合物在其循环伏安图中均显示，相对于FcH / FcH〜+，其电化学可逆的二茂铁基氧化范围为98≤E〜o'≤420 mV。在-1624≤E_（pc）≤-1102 mV的范围内观察到电化学和化学不可逆的Cu（II）还原。中性二茂铁基与氧化的，带正电的二茂铁阳离子之间的良好分子内通讯说明了良好解决的二茂铁基氧化还原过程。用线性方程E〜o'=98.5Σ_χ_R-629量化观察到的分子内通讯，该方程将形式二茂铁基氧化电位与R-基电负性总和Σ_χ_R相关。有可能表明，在[Cu（FcCOCHCOFc）_2]中，3d中，每个β-二酮基配体上的一个二茂铁基首先被氧化，然后同一β-二酮基配体上的第二个二茂铁基被氧化。在光谱电化学研究中，可以检测到电化学生成的3d混合价中间体的间歇电荷转移带（IVCT）。对于络合物3a，仅正常配体到金属的电荷转移带在约3。观察到650nm。这表明，在特定的β-二酮配体（例如（Fc〜+ COCHCOFc））中，Fc和Fc〜+基团之间的通信在3d内比在整个铜中心[Fc〜+ COCHCOR）Cu（FcCOCHCOR）]更有效。推测是因为跨整个铜中心的Fc？Fc〜+物种之间的距离比单个配体中的更长。

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