Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM3(OtBu)7] and [AnM2(OtBu)6] (AnIV = Th, U; MI = Li, Na, K, Rb, Cs)

Andreas Lichtenberg; Markus Zegke; Gary S. Nichol; Aida Raauf; Sanjay Mathur

doi:10.1039/d2dt01316a

Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM₃(O^tBu)₇] and [AnM₂(O^tBu)₆] (An^IV = Th, U; M^I = Li, Na, K, Rb, Cs)

Andreas Lichtenberg, Markus Zegke, Gary S. Nichol, Aida Raauf^*, Sanjay Mathur

^*Corresponding author for this work

School of Chemistry

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Abstract / Description of output

Heterobimetallic tert-butoxides of alkali metal cations with tetravalent actinide centers exhibit two distinctive structural motifs, [AnM₂(O^tBu)₆] and [AnM₃(O^tBu)₇] (An^IV = Th, U and M^I = Li, Na, K, Rb, Cs), evidently governed by the size of the alkali metal ions. Both [AnM₃(O^tBu)₇] AnM3 (An^IV = U, M^I = Li; An^IV = Th, M^I = Li, Na) and [AnM₂(O^tBu)₆] AnM2 (An^IV = U, M^I = Na-Cs; An^IV = Th, M^I = K-Cs) compounds are obtained in nearly quantitative yields by reacting actinide and alkali metal silyl amides with an excess of tert-butyl alcohol. The AnM3 complexes form a cubane-type coordination motif, whereas the AnM2 complexes display a geometry resembling two face-shared bipyramids. The sodium derivatives of thorium and uranium (ThNa3 and UNa2) allow the determination of the structural transition threshold as a function of the ratio of the ionic radii r_i(An^IV)/r_i(M^I). The AnM3 complexes are formed for ratios above 0.92 and the AnM2 type is formed for ratios below 0.87. All compounds are unambiguously characterized in both solution and solid states by NMR and IR spectroscopic studies and single crystal X-ray diffraction analyses, respectively.

Original language	English
Pages (from-to)	962-970
Number of pages	9
Journal	Dalton Transactions
Volume	52
Issue number	4
Early online date	4 Jan 2023
DOIs	https://doi.org/10.1039/d2dt01316a
Publication status	E-pub ahead of print - 4 Jan 2023

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20230104Nichold2dt01316aVoRFinal published version, 1.08 MBLicence: Creative Commons: Attribution (CC-BY)

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title = "Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM3(OtBu)7] and [AnM2(OtBu)6] (AnIV = Th, U; MI = Li, Na, K, Rb, Cs)",

abstract = "Heterobimetallic tert-butoxides of alkali metal cations with tetravalent actinide centers exhibit two distinctive structural motifs, [AnM2(OtBu)6] and [AnM3(OtBu)7] (AnIV = Th, U and MI = Li, Na, K, Rb, Cs), evidently governed by the size of the alkali metal ions. Both [AnM3(OtBu)7] AnM3 (AnIV = U, MI = Li; AnIV = Th, MI = Li, Na) and [AnM2(OtBu)6] AnM2 (AnIV = U, MI = Na-Cs; AnIV = Th, MI = K-Cs) compounds are obtained in nearly quantitative yields by reacting actinide and alkali metal silyl amides with an excess of tert-butyl alcohol. The AnM3 complexes form a cubane-type coordination motif, whereas the AnM2 complexes display a geometry resembling two face-shared bipyramids. The sodium derivatives of thorium and uranium (ThNa3 and UNa2) allow the determination of the structural transition threshold as a function of the ratio of the ionic radii ri(AnIV)/ri(MI). The AnM3 complexes are formed for ratios above 0.92 and the AnM2 type is formed for ratios below 0.87. All compounds are unambiguously characterized in both solution and solid states by NMR and IR spectroscopic studies and single crystal X-ray diffraction analyses, respectively.",

author = "Andreas Lichtenberg and Markus Zegke and Nichol, {Gary S.} and Aida Raauf and Sanjay Mathur",

note = "Funding Information: The authors cordially thank Dr Carsten Lenczyk and Dr Tobias St{\"u}rzer, both Bruker AXS Karlsruhe, for additional crystallographic advice and support, providing us with preliminary models for the modulated dataset URb2, the inversion twin dataset of ThNa3 and the merohedral twin dataset of ThCs2. We also thank Mr Dirk Pullem, University of Cologne, for CHNS measurements. Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

year = "2023",

month = jan,

day = "4",

doi = "10.1039/d2dt01316a",

language = "English",

volume = "52",

pages = "962--970",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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T1 - Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM3(OtBu)7] and [AnM2(OtBu)6] (AnIV = Th, U; MI = Li, Na, K, Rb, Cs)

AU - Lichtenberg, Andreas

AU - Zegke, Markus

AU - Nichol, Gary S.

AU - Raauf, Aida

AU - Mathur, Sanjay

N1 - Funding Information: The authors cordially thank Dr Carsten Lenczyk and Dr Tobias Stürzer, both Bruker AXS Karlsruhe, for additional crystallographic advice and support, providing us with preliminary models for the modulated dataset URb2, the inversion twin dataset of ThNa3 and the merohedral twin dataset of ThCs2. We also thank Mr Dirk Pullem, University of Cologne, for CHNS measurements. Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/1/4

Y1 - 2023/1/4

N2 - Heterobimetallic tert-butoxides of alkali metal cations with tetravalent actinide centers exhibit two distinctive structural motifs, [AnM2(OtBu)6] and [AnM3(OtBu)7] (AnIV = Th, U and MI = Li, Na, K, Rb, Cs), evidently governed by the size of the alkali metal ions. Both [AnM3(OtBu)7] AnM3 (AnIV = U, MI = Li; AnIV = Th, MI = Li, Na) and [AnM2(OtBu)6] AnM2 (AnIV = U, MI = Na-Cs; AnIV = Th, MI = K-Cs) compounds are obtained in nearly quantitative yields by reacting actinide and alkali metal silyl amides with an excess of tert-butyl alcohol. The AnM3 complexes form a cubane-type coordination motif, whereas the AnM2 complexes display a geometry resembling two face-shared bipyramids. The sodium derivatives of thorium and uranium (ThNa3 and UNa2) allow the determination of the structural transition threshold as a function of the ratio of the ionic radii ri(AnIV)/ri(MI). The AnM3 complexes are formed for ratios above 0.92 and the AnM2 type is formed for ratios below 0.87. All compounds are unambiguously characterized in both solution and solid states by NMR and IR spectroscopic studies and single crystal X-ray diffraction analyses, respectively.

AB - Heterobimetallic tert-butoxides of alkali metal cations with tetravalent actinide centers exhibit two distinctive structural motifs, [AnM2(OtBu)6] and [AnM3(OtBu)7] (AnIV = Th, U and MI = Li, Na, K, Rb, Cs), evidently governed by the size of the alkali metal ions. Both [AnM3(OtBu)7] AnM3 (AnIV = U, MI = Li; AnIV = Th, MI = Li, Na) and [AnM2(OtBu)6] AnM2 (AnIV = U, MI = Na-Cs; AnIV = Th, MI = K-Cs) compounds are obtained in nearly quantitative yields by reacting actinide and alkali metal silyl amides with an excess of tert-butyl alcohol. The AnM3 complexes form a cubane-type coordination motif, whereas the AnM2 complexes display a geometry resembling two face-shared bipyramids. The sodium derivatives of thorium and uranium (ThNa3 and UNa2) allow the determination of the structural transition threshold as a function of the ratio of the ionic radii ri(AnIV)/ri(MI). The AnM3 complexes are formed for ratios above 0.92 and the AnM2 type is formed for ratios below 0.87. All compounds are unambiguously characterized in both solution and solid states by NMR and IR spectroscopic studies and single crystal X-ray diffraction analyses, respectively.

U2 - 10.1039/d2dt01316a

DO - 10.1039/d2dt01316a

M3 - Article

C2 - 36597846

AN - SCOPUS:85145845461

SN - 1477-9226

VL - 52

SP - 962

EP - 970

JO - Dalton Transactions

JF - Dalton Transactions

IS - 4

ER -

Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM3(OtBu)7] and [AnM2(OtBu)6] (AnIV = Th, U; MI = Li, Na, K, Rb, Cs)

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Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM₃(O^tBu)₇] and [AnM₂(O^tBu)₆] (An^IV = Th, U; M^I = Li, Na, K, Rb, Cs)