Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster
Abstract Structurally characterised U−Sb bonds are rare. Here, the synthesis and characterisation of [U(TrenDMBS){Sb(H)C(H)(SiMe3)2}] (5, TrenDMBS=N(CH2CH2NSiMe2But)3) and [{U(TrenTIPS)}2{Sb3(μ6‐Li)(μ‐Li[THF]2)3Sb3}] (6, TrenTIPS=N(CH2CH2NSiPri3)3) are reported. Complex 5 is an unprecedented primary...
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Wiley-VCH
2023-11-01
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| 在線閱讀: | https://doi.org/10.1002/ceur.202300067 |
| _version_ | 1851924592235380736 |
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| author | Dr. Thomas M. Rookes Dr. Gábor Balázs Dr. Benedict M. Gardner Dr. Ashley J. Wooles Prof. Dr. Manfred Scheer Prof. Dr. Stephen T. Liddle |
| author_facet | Dr. Thomas M. Rookes Dr. Gábor Balázs Dr. Benedict M. Gardner Dr. Ashley J. Wooles Prof. Dr. Manfred Scheer Prof. Dr. Stephen T. Liddle |
| author_sort | Dr. Thomas M. Rookes |
| collection | DOAJ |
| container_title | ChemistryEurope |
| description | Abstract Structurally characterised U−Sb bonds are rare. Here, the synthesis and characterisation of [U(TrenDMBS){Sb(H)C(H)(SiMe3)2}] (5, TrenDMBS=N(CH2CH2NSiMe2But)3) and [{U(TrenTIPS)}2{Sb3(μ6‐Li)(μ‐Li[THF]2)3Sb3}] (6, TrenTIPS=N(CH2CH2NSiPri3)3) are reported. Complex 5 is an unprecedented primary stibinide actinide complex and 6 can be formulated as containing a unique triple decker 20 skeletal‐electron distorted closo tricapped Zintl cluster (Sb3Li4Sb3)2− that is analogous to the D3h closo tricapped trigonal prism form of [Ge9]2−. Quantum chemical calculations emphasise polar U−Sb bonding in 5 and 6, and that viewing (Sb3Li4Sb3)2− as a single unit rather than two distinct but contiguous (Sb3)3− units, themselves unprecedented in molecular actinide chemistry, is valid due to the presence of three weak (Sb3)⋯(Sb3) (3, −1)‐bond critical points. Complexes 5 and 6 highlight the challenges of preparing polar U−Sb bonds and the underlying tendency for unpredictable cluster formation with Sb. |
| format | Article |
| id | doaj-art-8773be8400a94bb3addec29c1816cd09 |
| institution | Directory of Open Access Journals |
| issn | 2751-4765 |
| language | English |
| publishDate | 2023-11-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| spelling | doaj-art-8773be8400a94bb3addec29c1816cd092025-08-19T21:56:58ZengWiley-VCHChemistryEurope2751-47652023-11-0113n/an/a10.1002/ceur.202300067Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl ClusterDr. Thomas M. Rookes0Dr. Gábor Balázs1Dr. Benedict M. Gardner2Dr. Ashley J. Wooles3Prof. Dr. Manfred Scheer4Prof. Dr. Stephen T. Liddle5Department of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UKInstitute of Inorganic Chemistry University of Regensburg Universitätsstr. 31 93053 Regensburg GermanyDepartment of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UKDepartment of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UKInstitute of Inorganic Chemistry University of Regensburg Universitätsstr. 31 93053 Regensburg GermanyDepartment of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UKAbstract Structurally characterised U−Sb bonds are rare. Here, the synthesis and characterisation of [U(TrenDMBS){Sb(H)C(H)(SiMe3)2}] (5, TrenDMBS=N(CH2CH2NSiMe2But)3) and [{U(TrenTIPS)}2{Sb3(μ6‐Li)(μ‐Li[THF]2)3Sb3}] (6, TrenTIPS=N(CH2CH2NSiPri3)3) are reported. Complex 5 is an unprecedented primary stibinide actinide complex and 6 can be formulated as containing a unique triple decker 20 skeletal‐electron distorted closo tricapped Zintl cluster (Sb3Li4Sb3)2− that is analogous to the D3h closo tricapped trigonal prism form of [Ge9]2−. Quantum chemical calculations emphasise polar U−Sb bonding in 5 and 6, and that viewing (Sb3Li4Sb3)2− as a single unit rather than two distinct but contiguous (Sb3)3− units, themselves unprecedented in molecular actinide chemistry, is valid due to the presence of three weak (Sb3)⋯(Sb3) (3, −1)‐bond critical points. Complexes 5 and 6 highlight the challenges of preparing polar U−Sb bonds and the underlying tendency for unpredictable cluster formation with Sb.https://doi.org/10.1002/ceur.202300067antimonyantimonidestibinideuraniumZintl cluster |
| spellingShingle | Dr. Thomas M. Rookes Dr. Gábor Balázs Dr. Benedict M. Gardner Dr. Ashley J. Wooles Prof. Dr. Manfred Scheer Prof. Dr. Stephen T. Liddle Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster antimony antimonide stibinide uranium Zintl cluster |
| title | Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster |
| title_full | Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster |
| title_fullStr | Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster |
| title_full_unstemmed | Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster |
| title_short | Actinide‐Pnictide Chemistry: A Uranium Primary Alkyl Stibinide and a Diuranium Hexaantimonide‐Tetralithium Zintl Cluster |
| title_sort | actinide pnictide chemistry a uranium primary alkyl stibinide and a diuranium hexaantimonide tetralithium zintl cluster |
| topic | antimony antimonide stibinide uranium Zintl cluster |
| url | https://doi.org/10.1002/ceur.202300067 |
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