Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores

Matthew A. Stuber, Anna Y. Kornienko, Thomas J. Emge, John G. Brennan

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Tetrametallic thorium compounds with a Th4E4 core (E = S, Se) having a distorted cubane structure can be prepared by ligand-based reductions of elemental E with thorium chalcogenolates, prepared by in situ oxidation of Th metal with a 3:1 mixture of PhEEPh and F5C6EEC6F5. Four compounds, (py)8Th4S42-SPh)4(SC6F5)4, (py)8Th4S42-SPh)4(SeC6F5)4, (py)8Th4Se42-SePh)4(SeC6F5)4, and (py)8Th4Se42-SePh)4(SC6F5)4, were isolated and characterized by NMR spectroscopy and X-ray diffraction. These compounds clearly demonstrate the chemical impact of ring fluorination, with the less-nucleophilic EC6F5 ligands occupying the terminal binding sites and the EPh ligands bridging two metal centers. For this series of compounds, crystal packing and intermolecular π⋯π and H-bonding interactions result in a consistent motif and crystallization in a body-centered tetragonal unit cell. Solution-state 77Se NMR spectroscopy reveals that the solid-state structures are maintained in pyridine.

Original languageEnglish (US)
Pages (from-to)10247-10256
Number of pages10
JournalInorganic Chemistry
Volume56
Issue number17
DOIs
StatePublished - Sep 5 2017

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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