Uranyl Analogue Complexes—Current Progress and Synthetic Challenges
Uranyl ions, {UO<sub>2</sub>}<sup>n+</sup> (n = 1, 2), display <i>trans</i>, strongly covalent, and chemically robust U-O multiple bonds, where 6d, 5f, and 6p orbitals play important roles. The synthesis of isoelectronic analogues of uranyl has been of interest fo...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-08-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/10/8/121 |
| _version_ | 1827617888171720704 |
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| author | Leonor Maria Joaquim Marçalo |
| author_facet | Leonor Maria Joaquim Marçalo |
| author_sort | Leonor Maria |
| collection | DOAJ |
| description | Uranyl ions, {UO<sub>2</sub>}<sup>n+</sup> (n = 1, 2), display <i>trans</i>, strongly covalent, and chemically robust U-O multiple bonds, where 6d, 5f, and 6p orbitals play important roles. The synthesis of isoelectronic analogues of uranyl has been of interest for quite some time, mainly with the purpose of unveiling covalence and 5f-orbital participation in bonding. Significant advances have occurred in the last two decades, initially marked by the synthesis of uranium(VI) bis(imido) complexes, the first analogues with a {RNUNR}<sup>2+</sup> core, later followed by the synthesis of unique <i>trans</i>-{EUO}<sup>2+</sup> (E = S, Se) complexes, and recently highlighted by the synthesis of the first complexes featuring a linear {NUN} moiety. This review covers the synthesis, structure, bonding, and reactivity of uranium complexes containing a linear {EUE}<sup>n+</sup> core (n = 0, 1, 2), isoelectronic to uranyl ions, {OUO}<sup>n+</sup> (n = 1, 2), incorporating σ- and π-donating ligands that can engage in uranium–ligand multiple bonding, where oxygen may be replaced by heavier chalcogenido, imido, nitride, and carbene ligands, or by a transition metal. It focuses on synthetic methods of well-defined molecular uranium species in the condensed phase but also references gas-phase and low-temperature-matrix experiments, as well as computational studies that may lead to valuable insights. |
| first_indexed | 2024-03-09T09:55:47Z |
| format | Article |
| id | doaj.art-def91cca77ac407296b5f3b7944a2be3 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-09T09:55:47Z |
| publishDate | 2022-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-def91cca77ac407296b5f3b7944a2be32023-12-01T23:49:17ZengMDPI AGInorganics2304-67402022-08-0110812110.3390/inorganics10080121Uranyl Analogue Complexes—Current Progress and Synthetic ChallengesLeonor Maria0Joaquim Marçalo1Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, 2695-066 Bobadela LRS, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, 2695-066 Bobadela LRS, PortugalUranyl ions, {UO<sub>2</sub>}<sup>n+</sup> (n = 1, 2), display <i>trans</i>, strongly covalent, and chemically robust U-O multiple bonds, where 6d, 5f, and 6p orbitals play important roles. The synthesis of isoelectronic analogues of uranyl has been of interest for quite some time, mainly with the purpose of unveiling covalence and 5f-orbital participation in bonding. Significant advances have occurred in the last two decades, initially marked by the synthesis of uranium(VI) bis(imido) complexes, the first analogues with a {RNUNR}<sup>2+</sup> core, later followed by the synthesis of unique <i>trans</i>-{EUO}<sup>2+</sup> (E = S, Se) complexes, and recently highlighted by the synthesis of the first complexes featuring a linear {NUN} moiety. This review covers the synthesis, structure, bonding, and reactivity of uranium complexes containing a linear {EUE}<sup>n+</sup> core (n = 0, 1, 2), isoelectronic to uranyl ions, {OUO}<sup>n+</sup> (n = 1, 2), incorporating σ- and π-donating ligands that can engage in uranium–ligand multiple bonding, where oxygen may be replaced by heavier chalcogenido, imido, nitride, and carbene ligands, or by a transition metal. It focuses on synthetic methods of well-defined molecular uranium species in the condensed phase but also references gas-phase and low-temperature-matrix experiments, as well as computational studies that may lead to valuable insights.https://www.mdpi.com/2304-6740/10/8/121uranyl analoguesuranium-ligand multiple bondingcovalencystructural parametersinverse <i>trans</i> influence |
| spellingShingle | Leonor Maria Joaquim Marçalo Uranyl Analogue Complexes—Current Progress and Synthetic Challenges Inorganics uranyl analogues uranium-ligand multiple bonding covalency structural parameters inverse <i>trans</i> influence |
| title | Uranyl Analogue Complexes—Current Progress and Synthetic Challenges |
| title_full | Uranyl Analogue Complexes—Current Progress and Synthetic Challenges |
| title_fullStr | Uranyl Analogue Complexes—Current Progress and Synthetic Challenges |
| title_full_unstemmed | Uranyl Analogue Complexes—Current Progress and Synthetic Challenges |
| title_short | Uranyl Analogue Complexes—Current Progress and Synthetic Challenges |
| title_sort | uranyl analogue complexes current progress and synthetic challenges |
| topic | uranyl analogues uranium-ligand multiple bonding covalency structural parameters inverse <i>trans</i> influence |
| url | https://www.mdpi.com/2304-6740/10/8/121 |
| work_keys_str_mv | AT leonormaria uranylanaloguecomplexescurrentprogressandsyntheticchallenges AT joaquimmarcalo uranylanaloguecomplexescurrentprogressandsyntheticchallenges |