Synthesis and Structure of an “Iron-Doped” Copper Selenide Cluster Molecule: [Cu30Fe2Se6(SePh)24(dppm)4]

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• 作者：Andreas Eichhfer ; Jolanta Olkowska-Oetzel ; Dieter Fenske ; Karin Fink ; Valeriu Mereacre ; Annie K. Powell ; Gernot Buth
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：September 21, 2009
• 年：2009
• 卷：48
• 期：18
• 页码：8977-8984
• 全文大小：870K
• 年卷期：v.48,no.18(September 21, 2009)
• ISSN：1520-510X

文摘

CuCl and bis(diphenylphosphanyl)methane (dppm) react in the presence of small amounts of FeCl₃ with PhSeSiMe₃ and Se(SiMe₃)₂ to yield [Cu₃₀Fe₂Se₆(SePh)₂₄(dppm)₄]. The crystal structure of the compound was determined by single-crystal X-ray analysis to give a mixed copper selenide/selenolate cluster molecule of a new structural type incorporating two central iron atoms. The formal oxidation state of the iron atoms was determined by Mssbauer spectroscopy to be +3, in agreement with quantum chemical calculations and modeling of the magnetic data. In addition, Mssbauer studies show no magnetic hyperfine structure in zero field, and the magnetically perturbed spectrum displays a pattern typical for a diamagnetic species in a transverse field, suggesting a singlet ground state. However, the inclusion of the iron atoms has a distinct influence on the optical properties of the compound compared to similar clusters containing only copper and selenium atoms.