Diversity of Functionalized Germanium Zintl Clusters: Syntheses and Theoretical Studies of [Ge9PdPPh3]3− and [Ni@(Ge9PdPPh3)]2−
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A new Zintl cluster [Ge9PdPPh3]3− has been isolated as (2,2,2-crypt)K+ salt through the reaction of K4Ge9 and Pd[PPh3]4 in ethylenediamine solutions and characterized via single-crystal X-ray crystallography. The as-prepared bimetallic [Ge9PdPPh3]3− cluster could successfully trap a nickel atom to form a trimetallic cluster [Ni@(Ge9PdPPh3)]2−. The coordination of Ge9 4− by PdPPh3 induces a one-electron oxidation and encapsulation of the Ni atom into the Ge9 3− cage leads to a further one-electron oxidation and a geometry transformation from C4v (nido) to C3v (closo).
KeywordsGermanium Cluster Stannaspherene Crystal structure Zintl ion
We thank Dr. Mike R. Thompson and Dr. Angel Ugrinov for help with the X-ray diffraction measurements and valuable discussions. The experimental work was supported by the National Science Foundation (DMR-0503383) and partially by the Petroleum Research Fund (PRF# 46275-AC6) administered by the American Chemical Society and performed at EMSL, a national scientific user facility sponsored by DOE¹s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, operated for DOE by Battelle. Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research. The theoretical work, supported by NKBRSF (2006CB932305, 2007CB815200) and NNSFC (20525104) in China, were performed using a HP Itanium2 cluster at Tsinghua National Laboratory for Information Science and Technology.
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