title: On the Nature of Bridging Metal Atoms in Intermetalloid Clusters: Synthesis and Structure of the Metal-Atom-Bridged Zintl Clusters [Sn(Ge9)2]4-and [Zn(Ge9)2)]6.
abstract: The addition of Sn and Zn ions to [Ge9] clusters by reaction of [Ge9]4-with SnPh2Cl2, ZnCp*2(Cp*=pentamethylcyclopentadienyl), or Zn2[HC(Ph2P=NPh)2]2is reported. The resulting Sn- and Zn-bridged clusters [(Ge9)M(Ge9)]q-(M=Sn, q=4; M=Zn, q=6) display various coordination modes. The M atoms that coordinate to the open square of a C4v-symmetric [Ge9] cluster form strong covalent multicenter M-Ge bonds, in contrast to the M atoms coordinating to triangular cluster faces. Molecular orbital analyses show that the M atoms of the Ge9M fragments coordinate to a second [Ge9] cluster with similar orbitals but in different ways. The [Ge9Sn]2-unit donates two electrons to the triangular face of a second [Ge9]2-cluster with D3hsymmetry, whereas [Ge9Zn]2-acts as an electron acceptor when interacting with the triangular face of a D3h-symmetric [Ge9]4-unit.
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Manuel M
authors.initials: MM
authors.lastname: Bentlohner
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Laura-Alice
authors.initials: LA
authors.lastname: Jantke
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Henneberger
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Christina
authors.initials: C
authors.lastname: Fischer
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Mayer
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
authors.forename: Wilhelm
authors.initials: W
authors.lastname: Klein
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany. thomas.faessler@lrz.tum.de.
authors.forename: Thomas F
authors.identifier: http://orcid.org/0000-0001-9460-8882
authors.initials: TF
authors.lastname: Fässler
keywords: Zintl anions; germanium; metal-metal interactions; tin; zinc