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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Isomerism and redox properties of 1-ferrocenyl-1,3-butanedionate complexes
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Isomerism and redox properties of 1-ferrocenyl-1,3-butanedionate complexes

机译:1-二茂铁基-1,3-丁二酸酯复合物的异构性和氧化还原性质

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The ferrocenyl diketone [(C5H5)Fe(C5H4)COCH2COCH3] has been used to form neutral metal complexes of the 1-ferrocenyl-1,3-butanedionate ligand [(C5H5)Fe(C5H4)COCHCOCH3](-): the aluminium complex of this ligand, [Al{(C5H5)Fe(C5H4)COCHCOCH3}(3)], has been characterised by H-1 and C-13 NMR as a 2:3 mixture of fac and mer isomers, having C-3 and C-1 molecular symmetry respectively. Electrochemical studies show that each peripheral 1-ferrocenyl-1,3-butanedionate ligand L of both (ML2)-L-II (M = Co, Ni, Cu) and (ML3)-L-III (M = Al, Cr, Mn, Fe) complexes undergoes reversible one-electron oxidation at potential values essentially overlapping each other. This means that the central metal ions prevent any electronic communication between the two or three ferrocene fragments. In addition to these reversible ferrocene-centred oxidations, there are reversible one-electron reductions centred at M for MnL3 and FeL3 (but not for CrL3 or AlL3), but the metal-centre reductions of (ML2)-L-II are irreversible owing to further reactions following reduction. (C) 1998 Elsevier Science Ltd. All rights reserved. [References: 19]
机译:二茂铁基二酮[((C5H5)Fe(C5H4)COCH2COCH3]已用于形成1-二茂铁基-1,3-丁二酸酯配体[(C5H5)Fe(C5H4)COCHCOCH3](-)的中性金属络合物:铝络合物该配体的[Al {(C5H5)Fe(C5H4)COCHCOCH3}(3)]通过H-1和C-13 NMR表征为fac和mer异构体的2:3混合物,具有C-3和C-1分子对称。电化学研究表明,(ML2)-L-II(M = Co,Ni,Cu)和(ML3)-L-III(M = Al,Cr, Mn,Fe)络合物在基本相互重叠的电势值下经历可逆的单电子氧化。这意味着中心金属离子阻止了两个或三个二茂铁片段之间的任何电子通讯。除了这些可逆的以二茂铁为中心的氧化外,MnL3和FeL3的可逆单电子还原中心在M处(但CrL3或AlL3则不这样),但由于(ML2)-L-II的金属中心还原是不可逆的还原后进一步反应。 (C)1998 Elsevier ScienceLtd。保留所有权利。 [参考:19]

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