The recently developed approach for the rational functionalization of deltahedral nona-germanium clusters Ge9(4-) with three substituents to form Ge9R3(-) (R = Si(SiMe3)3) in large amounts has made the latter a convenient starting material for further reactivity studies. Reported here are the synthesis, structures, and solution studies of two compounds where Ge9R3(-) are used as ligands to transition metals, [(Ge9R3)Cu(I)(Ge9R3)Cu(I)PPh3] (1) and [(Ge9R3)Pd(0)(Ge9R3)](2-) (2). The former adds to the families of anionic [(Ge9R3)M(I)(Ge9R3)](-) (M(I) = Cu, Ag, and Au) as a neutral member and of the neutral [(Ge9R3)M(II)(Ge9R3)] (M(II) = Zn, Cd, and Hg), while the latter represents the first compound involving a metal from group 10.
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[(Me3 Si)Si]3 EtGe9 Pd(PPh3 ), a Pentafunctionalized Deltahedral Zintl Cluster: Synthesis, Structure, and Solution Dynamics.
Angew Chem Int Ed Engl
July 2016
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, 46556, USA.
The title compound, which has a ten-atom deltahedral cluster core of Ge9 Pd, was synthesized through insertion of Pd(PPh3 ) into the tetrasubstituted nona-germanium cluster [(Me3 Si)Si]3 EtGe9 through a reaction of the latter with Pd(PPh3 )4 . This first reaction of neutral tetrasubstituted nine-atom clusters shows that they retain reactivity despite their neutral charge. The Ge9 Pd core is the first that incorporates a 5-connected transition metal other than from Group VI, a noble metal in this case.
View Article and Find Full Text PDFCoordination of Tri-Substituted Nona-Germanium Clusters to Cu(I) and Pd(0).
Inorg Chem
August 2015
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States.
The recently developed approach for the rational functionalization of deltahedral nona-germanium clusters Ge9(4-) with three substituents to form Ge9R3(-) (R = Si(SiMe3)3) in large amounts has made the latter a convenient starting material for further reactivity studies. Reported here are the synthesis, structures, and solution studies of two compounds where Ge9R3(-) are used as ligands to transition metals, [(Ge9R3)Cu(I)(Ge9R3)Cu(I)PPh3] (1) and [(Ge9R3)Pd(0)(Ge9R3)](2-) (2). The former adds to the families of anionic [(Ge9R3)M(I)(Ge9R3)](-) (M(I) = Cu, Ag, and Au) as a neutral member and of the neutral [(Ge9R3)M(II)(Ge9R3)] (M(II) = Zn, Cd, and Hg), while the latter represents the first compound involving a metal from group 10.
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