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

doi:10.1021/acs.inorgchem.8b00836

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

School of Arts and Sciences, Chemistry & Chemical Biology

Research output: Contribution to journal › Article

3 Scopus citations

Abstract

Thorium cubanes (py)₈Th₄(μ₃-E′)₄(μ₂-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)₈Th₄(μ₃-S)₄(μ₂-SePh)₄(ν-SePh)₄ and (py)₈Th₄(μ₃-Se)₄(μ₂-SPh)₄(ν-SPh)₄ were heated to deliver solid solutions of ThS_xSe_2-x. NMR spectroscopy indicated that the structure of (py)₈Th₄(μ₃-Se)₄(μ₂-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 language	English (US)
Pages (from-to)	7129-7141
Number of pages	13
Journal	Inorganic Chemistry
Volume	57
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00836
State	Published - Jun 18 2018

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.8b00836

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Ringgold, M., Rehe, D., Hrobárik, P., Kornienko, A. Y., Emge, T. J., & Brennan, J. G. (2018). Thorium Cubanes-Synthesis, Solid-State and Solution Structures, Thermolysis, and Chalcogen Exchange Reactions. Inorganic Chemistry, 57(12), 7129-7141. https://doi.org/10.1021/acs.inorgchem.8b00836

@article{857acf3253624c3fb6324c5768385d67,

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

abstract = "Thorium cubanes (py)8Th4(μ3-E′)4(μ2-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)8Th4(μ3-S)4(μ2-SePh)4(ν-SePh)4 and (py)8Th4(μ3-Se)4(μ2-SPh)4(ν-SPh)4 were heated to deliver solid solutions of ThSxSe2-x. NMR spectroscopy indicated that the structure of (py)8Th4(μ3-Se)4(μ2-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.",

author = "Marissa Ringgold and David Rehe and Peter Hrob{\'a}rik and Kornienko, {Anna Y.} and Emge, {Thomas J.} and Brennan, {John G.}",

year = "2018",

month = jun,

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doi = "10.1021/acs.inorgchem.8b00836",

language = "English (US)",

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journal = "Inorganic Chemistry",

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T1 - Thorium Cubanes-Synthesis, Solid-State and Solution Structures, Thermolysis, and Chalcogen Exchange Reactions

AU - Ringgold, Marissa

AU - Rehe, David

AU - Hrobárik, Peter

AU - Kornienko, Anna Y.

AU - Emge, Thomas J.

AU - Brennan, John G.

PY - 2018/6/18

Y1 - 2018/6/18

N2 - Thorium cubanes (py)8Th4(μ3-E′)4(μ2-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)8Th4(μ3-S)4(μ2-SePh)4(ν-SePh)4 and (py)8Th4(μ3-Se)4(μ2-SPh)4(ν-SPh)4 were heated to deliver solid solutions of ThSxSe2-x. NMR spectroscopy indicated that the structure of (py)8Th4(μ3-Se)4(μ2-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.

AB - Thorium cubanes (py)8Th4(μ3-E′)4(μ2-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)8Th4(μ3-S)4(μ2-SePh)4(ν-SePh)4 and (py)8Th4(μ3-Se)4(μ2-SPh)4(ν-SPh)4 were heated to deliver solid solutions of ThSxSe2-x. NMR spectroscopy indicated that the structure of (py)8Th4(μ3-Se)4(μ2-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.

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