Addition of a thallium vertex to empty and centered nine-atom deltahedral zintl ions of germanium and tin

Daniel Rios; Miriam M Gillett-Kunnath; Jacob D Taylor; Allen G Oliver; Slavi C Sevov

doi:10.1021/ic102152e

Addition of a thallium vertex to empty and centered nine-atom deltahedral zintl ions of germanium and tin

Inorg Chem. 2011 Mar 21;50(6):2373-7. doi: 10.1021/ic102152e. Epub 2011 Feb 4.

Authors

Daniel Rios¹, Miriam M Gillett-Kunnath, Jacob D Taylor, Allen G Oliver, Slavi C Sevov

Affiliation

¹ Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States.

PMID: 21294520
DOI: 10.1021/ic102152e

Abstract

Nickel atoms were inserted into nine-atom deltahedral Zintl ions of E(9)(4-) (E = Ge, Sn) via reactions with Ni(cod)(2) (cod = cyclooctadiene), and [Ni@Sn(9)](3-) was structurally characterized. Both the empty and the Ni-centered clusters react with TlCp (Cp = cyclopentadienyl anion) and add a thallium vertex to form the deltahedral ten-atom closo-species [E(9)Tl](3-) and [Ni@E(9)Tl](3-), respectively. The structures of [Ge(9)Tl](3-) and [Ni@Sn(9)Tl](3-) showed that, as expected, the geometry of the ten-atom clusters is that of a bicapped square antiprism where the Tl-atom occupies one of the two capping vertices. This illustrates that centering a nine-atom cluster with a nickel atom does not change its reactivity toward TlCp. All compounds were characterized by electrospray mass spectrometry.