f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1– Affords the Trithorium and Triuranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(μ3-Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSiiPr3)3}3–) DOI Creative Commons
Jingzhen Du, Kevin Dollberg, John A. Seed

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20153 - 20160

Published: May 20, 2024

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

Language: Английский

f-Element Zintl Chemistry: Actinide-Mediated Dehydrocoupling of H2Sb1– Affords the Trithorium and Triuranium Undeca-Antimontriide Zintl Clusters [{An(TrenTIPS)}3(μ3-Sb11)] (An = Th, U; TrenTIPS = {N(CH2CH2NSiiPr3)3}3–) DOI Creative Commons
Jingzhen Du, Kevin Dollberg, John A. Seed

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20153 - 20160

Published: May 20, 2024

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

Language: Английский

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