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

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

doi:10.1021/acs.inorgchem.7b00950

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

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

School of Arts and Sciences, Chemistry & Chemical Biology

Research output: Contribution to journal › Article › peer-review

5 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)₈Th₄S₄(μ₂-SPh)₄(SC₆F₅)₄, (py)₈Th₄S₄(μ₂-SPh)₄(SeC₆F₅)₄, (py)₈Th₄Se₄(μ₂-SePh)₄(SeC₆F₅)₄, and (py)₈Th₄Se₄(μ₂-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 language	English (US)
Pages (from-to)	10247-10256
Number of pages	10
Journal	Inorganic Chemistry
Volume	56
Issue number	17
DOIs	https://doi.org/10.1021/acs.inorgchem.7b00950
State	Published - Sep 5 2017

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.7b00950

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

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)8Th4S4(μ2-SPh)4(SC6F5)4, (py)8Th4S4(μ2-SPh)4(SeC6F5)4, (py)8Th4Se4(μ2-SePh)4(SeC6F5)4, and (py)8Th4Se4(μ2-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.",

author = "Stuber, {Matthew A.} and Kornienko, {Anna Y.} and Emge, {Thomas J.} and Brennan, {John G.}",

note = "Funding Information: This material is based upon work supported by the National Science Foundation under CHE 1464887. We thank S. Hayes (Washington Univ.) for helpful discussions and M. Ringgold (Rutgers Univ.) for providing 77Se NMR data for (py)3Th(SePh)4. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.7b00950",

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T1 - Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores

AU - Stuber, Matthew A.

AU - Kornienko, Anna Y.

AU - Emge, Thomas J.

AU - Brennan, John G.

N1 - Funding Information: This material is based upon work supported by the National Science Foundation under CHE 1464887. We thank S. Hayes (Washington Univ.) for helpful discussions and M. Ringgold (Rutgers Univ.) for providing 77Se NMR data for (py)3Th(SePh)4. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/9/5

Y1 - 2017/9/5

N2 - 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)8Th4S4(μ2-SPh)4(SC6F5)4, (py)8Th4S4(μ2-SPh)4(SeC6F5)4, (py)8Th4Se4(μ2-SePh)4(SeC6F5)4, and (py)8Th4Se4(μ2-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.

AB - 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)8Th4S4(μ2-SPh)4(SC6F5)4, (py)8Th4S4(μ2-SPh)4(SeC6F5)4, (py)8Th4Se4(μ2-SePh)4(SeC6F5)4, and (py)8Th4Se4(μ2-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.

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ER -

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

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