Thorium Cubanes-Synthesis, Solid-State and Solution Structures, Thermolysis, and Chalcogen Exchange Reactions

Marissa Ringgold, David Rehe, Peter Hrobárik, Anna Y. Kornienko, Thomas J. Emge, John G. Brennan

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

Thorium cubanes (py)8Th43-E′)42-EPh)4(ν-EPh)4 (E, E′ = S, Se) were prepared from ligand-based redox reactions of elemental E′ with Th(EPh)4. Products with all four possible E/E′ combinations (E,E′ = S,S; Se,Se; S,Se; Se,S) were isolated and structurally characterized, ligand exchange reactions were explored, and the heterochalcogen compounds (py)8Th43-S)42-SePh)4(ν-SePh)4 and (py)8Th43-Se)42-SPh)4(ν-SPh)4 were heated to deliver solid solutions of ThSxSe2-x. NMR spectroscopy indicated that the structure of (py)8Th43-Se)42-SePh)4(ν-SePh)4 is static in pyridine solution, with no exchange between bridging and terminal PhE- ligands on the NMR time scale. A computational analysis of 77Se NMR shifts provides insight into the solution structure of both clusters and monomeric chalcogenolates.

Original languageEnglish (US)
Pages (from-to)7129-7141
Number of pages13
JournalInorganic Chemistry
Volume57
Issue number12
DOIs
StatePublished - Jun 18 2018

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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