Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding
Abstract Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actin...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-39626-8 |
| _version_ | 1797774126186758144 |
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| author | Laura C. Motta Jochen Autschbach |
| author_facet | Laura C. Motta Jochen Autschbach |
| author_sort | Laura C. Motta |
| collection | DOAJ |
| description | Abstract Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actinide-ligand covalent interactions with high bond multiplicities quantifies the energetic contributions from PFB and identifies a hitherto overlooked fourth bonding interaction for 2nd-row ligands in the studied organometallic systems. The latter are best described by a terminal O/N ligand exhibiting quadruple bonding interactions with the actinide. The 4th interaction may be characterized as a multi-center or charge-shift bond involving the trans ligand. It is shown in this work that the 4th bonding interaction is a manifestation of ITI, assisted by PFB, and provides a long-sought missing piece in the understanding of actinide chemistry. |
| first_indexed | 2024-03-12T22:16:27Z |
| format | Article |
| id | doaj.art-fccdeccbd6f340e2ac7a632df8045056 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-12T22:16:27Z |
| publishDate | 2023-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-fccdeccbd6f340e2ac7a632df80450562023-07-23T11:19:23ZengNature PortfolioNature Communications2041-17232023-07-0114111010.1038/s41467-023-39626-8Actinide inverse trans influence versus cooperative pushing from below and multi-center bondingLaura C. Motta0Jochen Autschbach1Department of Chemistry, University at Buffalo, State University of New YorkDepartment of Chemistry, University at Buffalo, State University of New YorkAbstract Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actinide-ligand covalent interactions with high bond multiplicities quantifies the energetic contributions from PFB and identifies a hitherto overlooked fourth bonding interaction for 2nd-row ligands in the studied organometallic systems. The latter are best described by a terminal O/N ligand exhibiting quadruple bonding interactions with the actinide. The 4th interaction may be characterized as a multi-center or charge-shift bond involving the trans ligand. It is shown in this work that the 4th bonding interaction is a manifestation of ITI, assisted by PFB, and provides a long-sought missing piece in the understanding of actinide chemistry.https://doi.org/10.1038/s41467-023-39626-8 |
| spellingShingle | Laura C. Motta Jochen Autschbach Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding Nature Communications |
| title | Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding |
| title_full | Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding |
| title_fullStr | Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding |
| title_full_unstemmed | Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding |
| title_short | Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding |
| title_sort | actinide inverse trans influence versus cooperative pushing from below and multi center bonding |
| url | https://doi.org/10.1038/s41467-023-39626-8 |
| work_keys_str_mv | AT lauracmotta actinideinversetransinfluenceversuscooperativepushingfrombelowandmulticenterbonding AT jochenautschbach actinideinversetransinfluenceversuscooperativepushingfrombelowandmulticenterbonding |