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Synthesis of Ge2NiS4 Clusters and the Thermal Transformation to a Ge4Ni6S12 Cluster

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Version 1 2016-02-27, 17:14
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posted on 2008-03-17, 00:00 authored by Tsuyoshi Matsumoto, Yosuke Matsui, Mikinao Ito, Kazuyuki Tatsumi
The reaction of Ni(dppe)Cl2 and syn-[DmpGe(SLi)(μ-S)2Ge(SLi)Dmp] prepared in situ from syn-[DmpGe(SH)(μ-S)2Ge(SH)Dmp] (1) and n-BuLi (2 equiv) afforded the Ge2NiS4 cluster, [DmpGe(μ-S)]2(μ-S)2Ni(dppe) (2) (Dmp = 2,6-dimesitylphenyl). The nickel in 2 assumes a slightly distorted square planar geometry. However, another Ge2NiS4 cluster, [DmpGe(μ-S)]2(μ-S)2Ni(PPh3)2 (3) obtained from a similar reaction with Ni(PPh3)2Cl2, contains the nickel in a tetrahedron. When 3 was heated to 120 °C in toluene, a novel Ge4Ni6S12 cluster [DmpGe(μ-S)3]4Ni6 (5) was obtained. In cluster 5, six nickels form an octahedron with the nickels occupying its vertexes, and four DmpGeS3 units cap half of the trigonal faces.

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