Uranium Hexamethoxide and Mixed Methoxyuranium(VI) Fluorides: Facile Syntheses from UF6 and a Nuclear Magnetic Resonance Investigation of Structure and Chemical Dynamics

Edward A. Cuellar; Tobin J. Marks

doi:10.1021/ic50221a037

Uranium Hexamethoxide and Mixed Methoxyuranium(VI) Fluorides: Facile Syntheses from UF₆ and a Nuclear Magnetic Resonance Investigation of Structure and Chemical Dynamics

Edward A. Cuellar, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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

2 Scopus citations

Abstract

Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

Original language	English (US)
Pages (from-to)	2129-2137
Number of pages	9
Journal	Inorganic chemistry
Volume	20
Issue number	7
DOIs	https://doi.org/10.1021/ic50221a037
State	Published - Jul 1981

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Uranium Hexamethoxide and Mixed Methoxyuranium(VI) Fluorides: Facile Syntheses from UF6 and a Nuclear Magnetic Resonance Investigation of Structure and Chemical Dynamics",

abstract = "Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.",

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year = "1981",

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AU - Marks, Tobin J.

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Y1 - 1981/7

N2 - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

AB - Efficient, one-step scalable syntheses of uranium hexamethoxide, U(OCH3)6, starting from readily available UF6 and NaOCH3 or CH3Si(OCH3)3 are described. In addition, the reaction of appropriate quantities of (CH3)3SiOCH3 or U(OCH3)6 with UF6 produces a series of mixed methoxyuranium(VI) fluorides, U(OCH3)nF6-n = 1-5, the degree of substitution being determined by control of stoichiometry. Characterization of the complexes by both and 19F NMR indicates that all the species possess a monomeric, six-coordinate geometry and undergo rapid, intermolecular ligand exchange. A surprisingly large solvent and temperature dependence of the 19F chemical shifts is interpreted in terms of charge-transfer complex formation. The solution-phase electronic spectrum of U(OCH3)6 is interpreted in terms of both ligand- and solvent-to-metal charge transfer.

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Uranium Hexamethoxide and Mixed Methoxyuranium(VI) Fluorides: Facile Syntheses from UF₆ and a Nuclear Magnetic Resonance Investigation of Structure and Chemical Dynamics

Abstract

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