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The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes
Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside tran...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5296655/ https://www.ncbi.nlm.nih.gov/pubmed/28155857 http://dx.doi.org/10.1038/ncomms14137 |
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author | Gregson, Matthew Lu, Erli Mills, David P. Tuna, Floriana McInnes, Eric J. L. Hennig, Christoph Scheinost, Andreas C. McMaster, Jonathan Lewis, William Blake, Alexander J. Kerridge, Andrew Liddle, Stephen T. |
author_facet | Gregson, Matthew Lu, Erli Mills, David P. Tuna, Floriana McInnes, Eric J. L. Hennig, Christoph Scheinost, Andreas C. McMaster, Jonathan Lewis, William Blake, Alexander J. Kerridge, Andrew Liddle, Stephen T. |
author_sort | Gregson, Matthew |
collection | PubMed |
description | Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle. |
format | Online Article Text |
id | pubmed-5296655 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | Nature Publishing Group |
record_format | MEDLINE/PubMed |
spelling | pubmed-52966552017-02-22 The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes Gregson, Matthew Lu, Erli Mills, David P. Tuna, Floriana McInnes, Eric J. L. Hennig, Christoph Scheinost, Andreas C. McMaster, Jonathan Lewis, William Blake, Alexander J. Kerridge, Andrew Liddle, Stephen T. Nat Commun Article Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle. Nature Publishing Group 2017-02-03 /pmc/articles/PMC5296655/ /pubmed/28155857 http://dx.doi.org/10.1038/ncomms14137 Text en Copyright © 2017, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Article Gregson, Matthew Lu, Erli Mills, David P. Tuna, Floriana McInnes, Eric J. L. Hennig, Christoph Scheinost, Andreas C. McMaster, Jonathan Lewis, William Blake, Alexander J. Kerridge, Andrew Liddle, Stephen T. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title | The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title_full | The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title_fullStr | The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title_full_unstemmed | The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title_short | The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
title_sort | inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5296655/ https://www.ncbi.nlm.nih.gov/pubmed/28155857 http://dx.doi.org/10.1038/ncomms14137 |
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