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

• Published in: Inorganic chemistry 2018-06, Vol.57 (12), p.7129-7141
• Main Authors: Ringgold, Marissa, Rehe, David, Hrobárik, Peter, Kornienko, Anna Y, Emge, Thomas J, Brennan, John G
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.8b00836

Thorium cubanes (py)8Th4(μ3-E′)4(μ2-EPh)4(η-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)8Th4(μ3-S)4­(μ2-SePh)4­(η-SePh)4 and (py)8Th4(μ3-Se)4­(μ2-SPh)4­(η-SPh)4 were heated to deliver solid solutions of ThS x Se2–x . NMR spectroscopy indicated that the structure of (py)8Th4­(μ3-Se)4­(μ2-SePh)4­(η-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.