f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1- Affords the Tri-Thorium and -Uranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(µ3- Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSii Pr3)3}3-)

Jingzhen Du; Kevin  Dollberg; John Seed; Ashley Wooles; Carsten  von Hänisch; Stephen Liddle

f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H₂Sb^1- Affords the Tri-Thorium and -Uranium Undeca-Antimontriide Zintl Clusters [{An(Tren^TIPS)}₃(µ₃- Sb₁₁)] (An = Th, U; Tren^TIPS = {N(CH₂CH₂NSiⁱ Pr₃)₃}^3-)

Jingzhen Du, Kevin Dollberg, John Seed, Ashley Wooles, Carsten von Hänisch, Stephen Liddle

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

Abstract

Reaction of the cesium antimonide complex [Cs(18C6)₂][SbH₂] (1, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(Tren^TIPS)(L)][BPh₄] (Tren^TIPS = {N(CH₂CH₂NSiⁱPr₃)₃}^3-; An/L = Th/DME (2Th); U/THF (2U)) affords the triactinide undeca-antimontriide Zintl clusters [{An(Tren^TIPS)}₃(µ₃-Sb₁₁)] (An = Th (3Th), U (3U)) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb₁₁^3- Zintl trianion, and unprecedented examples of molecular Sb₁₁^3- being coordinated to anything since all previous reports featured isolated Sb₁₁^3- Zintl trianions in separated ion quadruple formulations with non-coordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U, though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/Vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.

Original language	English
Journal	Inorganic Chemistry
Publication status	Accepted/In press - 7 May 2024

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An3Sb11_Paper
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@article{3b52b11394694d18881b8ced702eb73b,

title = "f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1- Affords the Tri-Thorium and -Uranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(µ3- Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSii Pr3)3}3-)",

abstract = "Reaction of the cesium antimonide complex [Cs(18C6)2][SbH2] (1, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(TrenTIPS)(L)][BPh4] (TrenTIPS = {N(CH2CH2NSiiPr3)3}3-; An/L = Th/DME (2Th); U/THF (2U)) affords the triactinide undeca-antimontriide Zintl clusters [{An(TrenTIPS)}3(µ3-Sb11)] (An = Th (3Th), U (3U)) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb113- Zintl trianion, and unprecedented examples of molecular Sb113- being coordinated to anything since all previous reports featured isolated Sb113- Zintl trianions in separated ion quadruple formulations with non-coordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U, though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/Vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.",

author = "Jingzhen Du and Kevin Dollberg and John Seed and Ashley Wooles and {von H{\"a}nisch}, Carsten and Stephen Liddle",

year = "2024",

month = may,

day = "7",

language = "English",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

}

f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H₂Sb^1- Affords the Tri-Thorium and -Uranium Undeca-Antimontriide Zintl Clusters [{An(Tren^TIPS)}₃(µ₃- Sb₁₁)] (An = Th, U; Tren^TIPS = {N(CH₂CH₂NSiⁱ Pr₃)₃}^3-). / Du, Jingzhen; Dollberg, Kevin ; Seed, John et al.
In: Inorganic Chemistry, 07.05.2024.

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

TY - JOUR

T1 - f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1- Affords the Tri-Thorium and -Uranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(µ3- Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSii Pr3)3}3-)

AU - Du, Jingzhen

AU - Dollberg, Kevin

AU - Seed, John

AU - Wooles, Ashley

AU - von Hänisch, Carsten

AU - Liddle, Stephen

PY - 2024/5/7

Y1 - 2024/5/7

N2 - Reaction of the cesium antimonide complex [Cs(18C6)2][SbH2] (1, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(TrenTIPS)(L)][BPh4] (TrenTIPS = {N(CH2CH2NSiiPr3)3}3-; An/L = Th/DME (2Th); U/THF (2U)) affords the triactinide undeca-antimontriide Zintl clusters [{An(TrenTIPS)}3(µ3-Sb11)] (An = Th (3Th), U (3U)) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb113- Zintl trianion, and unprecedented examples of molecular Sb113- being coordinated to anything since all previous reports featured isolated Sb113- Zintl trianions in separated ion quadruple formulations with non-coordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U, though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/Vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.

AB - Reaction of the cesium antimonide complex [Cs(18C6)2][SbH2] (1, 18C6 = 18-crown-6 ether) with the triamidoamine actinide separated ion pairs [An(TrenTIPS)(L)][BPh4] (TrenTIPS = {N(CH2CH2NSiiPr3)3}3-; An/L = Th/DME (2Th); U/THF (2U)) affords the triactinide undeca-antimontriide Zintl clusters [{An(TrenTIPS)}3(µ3-Sb11)] (An = Th (3Th), U (3U)) by dehydrocoupling. Clusters 3Th and 3U provide two new examples of the Sb113- Zintl trianion, and unprecedented examples of molecular Sb113- being coordinated to anything since all previous reports featured isolated Sb113- Zintl trianions in separated ion quadruple formulations with non-coordinating cations. Quantum chemical calculations describe dominant ionic An-Sb interactions in 3Th and 3U, though the data suggest that the latter exhibits slightly more covalent An-Sb linkages than the former. Complexes 3Th and 3U have been characterized by single crystal X-ray diffraction, NMR, IR, and UV/Vis/NIR spectroscopies, elemental analysis, and quantum chemical calculations.

M3 - Article

SN - 0020-1669

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -