title: Synthesis of Ge2NiS4 clusters and the thermal transformation to a Ge4Ni6S12 cluster.
abstract: The reaction of Ni(dppe)Cl2 and syn-[DmpGe(SLi)(mu-S)2Ge(SLi)Dmp] prepared in situ from syn-[DmpGe(SH)(mu-S)2Ge(SH)Dmp] (1) and n-BuLi (2 equiv) afforded the Ge2NiS4 cluster, [DmpGe(mu-S)]2(mu-S)2Ni(dppe) (2) (Dmp = 2,6-dimesitylphenyl). The nickel in 2 assumes a slightly distorted square planar geometry. However, another Ge2NiS4 cluster, [DmpGe(mu-S)]2(mu-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 degrees C in toluene, a novel Ge4Ni6S12 cluster [DmpGe(mu-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.
authors.affiliation: Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan.
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Matsumoto
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Matsui
authors.forename: Mikinao
authors.initials: M
authors.lastname: Ito
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
mesh_terms: D005857:Germanium / Q000737:chemistry*; D008667:Metalloproteins / Q000737:chemistry; D009532:Nickel / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D008667:Metalloproteins; D005857:Germanium; D013455:Sulfur; D009532:Nickel