Synthesis of syn‐2,4‐Dimercapto‐1,3,2,4‐dithiadigermetane and Its Application to Ge2PdS4 Cluster Synthesis |
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Authors: | Tsuyoshi Matsumoto Dr. Yosuke Matsui Mikinao Ito Kazuyuki Tatsumi Prof. Dr. |
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Affiliation: | Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Furo‐cho, Chikusa‐ku, Nagoya 464‐8602, Japan, Fax: (+81)?52‐789‐2943 |
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Abstract: | The sulfurization of DmpGeH3 (Dmp=2,6‐dimesitylphenyl) afforded the trinuclear germanium sulfide [DmpGe(μ‐S)]2(μ‐S)2Ge(SH)‐Dmp and a series of polythiadigermabicyclo[x.1.1]alkanes (x=3, 4, 5). The reduction of the S? S bonds of these germabicycloalkanes by NaBH4 at 0 °C afforded the dinuclear mercaptogermane syn‐[DmpGe(SH)(μ‐S)2Ge(SH)‐Dmp] ( 5 ) in good yield. The reaction of [Pd(dppe)Cl2] (dppe=1,2‐bis(diphenylphosphanyl)ethane) and the dilithium salt of 5 prepared in situ by the addition of nBuLi (2 equiv) gave the Ge2PdS4 cluster [DmpGe(μ‐S)]2[(μ‐S)2Pd(dppe)], in which the dithiadigermetanedithiolate is bound to the Pd atom at the two thiolato sulfur atoms. The same reaction with [Pd(PPh3)2Cl2] gave another Ge2PdS4 cluster, [DmpGe(μ‐S)]2[(μ‐S)2Pd(PPh3)], but with the dithiadigermetanedithiolate and the Pd center conjoined through a μ‐S atom between the two germanium atoms in addition to the two thiolato sulfur atoms to form a highly distorted cluster core. The formation of two different types of Ge2PdS4 clusters represents the usefulness of 5 in the synthesis of various polynuclear complexes composed of germanium and transition metals. |
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Keywords: | germanium metal sulfides palladium polychalcogenides polynuclear complexes |
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