Mössbauer study and molecular orbital calculations on some bimetallic derivatives of ferrocene and ferricinium
Mössbauer study and molecular orbital calculations on some bimetallic derivatives of ferrocene and ferricinium
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二茂铁和二茂铁的一些双金属衍生物的穆斯堡尔研究和分子轨道计算
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
F. Varret
中科院分区：
文献类型：
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作者：
H. Rabah;J. Guillin;Annie Cereze;J. Greneche;D. Talham;K. Boukheddaden;J. Linares;F. Varret
本文用穆斯堡尔吸收光谱法研究了未氧化（Fe Ⅱ-Fe Ⅱ）和单氧化（Fe Ⅱ-Fe Ⅲ）的联二茂铁桥联衍生物。混合价态物质在穆斯堡尔时间尺度（10−8 s）表现出准离域行为，谱线分裂，解释为部分价态俘获。这反过来又揭示了分子内性质的差异，从那些未桥接的阳离子。SCC-Xα MO计算结果正确地再现了四重分裂的测量结果，并证明了混合价络合物的HOMO是
$$d_{xy}，d_{x^2 - y^2 } $$
类型.一些后果的混合价属性进行了讨论。
AbstractWe have studied by absorption Mössbauer spectroscopy, some bridged derivatives of biferrocene, unoxidized (FeII– FeII) and mono-oxidized (FeII – FeIII). The mixed-valence species exhibits a quasi-delocalized behavior at the Mössbauer timescale (∼ 10−8 s), with a splitting of the lines which is interpreted in terms of a partial valence trapping. This in turn reveals intramolecular properties at variance from those of the unbridged cation. SCC-Xα MO calculations have been performed; they correctly reproduce the measured quadruple splittings and provide evidence that the HOMO of the mixed-valence complex is of
$$d_{xy} ,d_{x^2 - y^2 } $$
type. Some consequences on the mixed-valence properties are discussed.