Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands

In the coordination chemistry of heavier tetrylenes (:ER2, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R2P-NR']-, have been barely investigated. Herein, we report the synthesis and structural characterization of such compl...

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Autores: Bajo, Sonia, Fernández-Buenestado, Marta, López-Serrano, Joaquín, Campos, Jesús
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/414463
Acesso em linha:http://hdl.handle.net/10261/414463
https://api.elsevier.com/content/abstract/scopus_id/105024756264
Access Level:acceso abierto
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spelling Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido LigandsBajo, SoniaFernández-Buenestado, MartaLópez-Serrano, JoaquínCampos, JesúsIn the coordination chemistry of heavier tetrylenes (:ER2, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R2P-NR']-, have been barely investigated. Herein, we report the synthesis and structural characterization of such complexes, whose structures drastically differ depending on the group 9 metal precursor used. Strained four-membered {P-N-Ge-M} metallacycles (M = Rh, Ir) are produced from the reaction of phosphinoamido germylenes with [MCl2Cp*]2 precursors (Cp* = η5-C5Me5). At variance, [MCl-(COD)]2 dimers are not broken apart; instead, they afford bimetallic species featuring bridging phosphinoamido-germyl and chloride ligands between the two metals. All new compounds were isolated on a preparative scale and spectroscopically characterized and their structures confirmed by X-ray diffraction. Computational studies support the σ-donor character of the Ge-M interaction and the absence of significant π-backbonding.This work was funded by the European Union (ERC Consolidator Grant, BiMetalGAS, 101169746) and the Spanish MCIU/AEI/10.13039/501100011033 (Grant PID2022-139782NB-I00). The use of computational facilities of the Galicia Supercomputing Centre (CESGA, Cluster Finisterrae-III) are thankfully acknowledged.Peer reviewedAmerican Chemical SocietyEuropean CommissionMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)López-Serrano, Joaquín [0000-0003-3999-0155]Campos, Jesús [0000-0002-5155-1262]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202620262025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/414463https://api.elsevier.com/content/abstract/scopus_id/105024756264reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139782NB-I00Bajo, Sonia; Fernández-Buenestado, Marta; López-Serrano, Joaquín; Campos, Jesús;2025; Supporting Information:Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands; Figshare; https://doi.org/10.1021/acs.organomet.5c00403.s001Bajo, Sonia; Fernández-Buenestado, Marta; López-Serrano, Joaquín; Campos, Jesús;2025; Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands [Dataset]; Figshare; https://doi.org/10.1021/acs.organomet.5c00403.s002http://dx.doi.org/10.1021/acs.organomet.5c00403Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4144632026-05-22T06:33:51Z
dc.title.none.fl_str_mv Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
title Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
spellingShingle Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
Bajo, Sonia
title_short Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
title_full Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
title_fullStr Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
title_full_unstemmed Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
title_sort Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
dc.creator.none.fl_str_mv Bajo, Sonia
Fernández-Buenestado, Marta
López-Serrano, Joaquín
Campos, Jesús
author Bajo, Sonia
author_facet Bajo, Sonia
Fernández-Buenestado, Marta
López-Serrano, Joaquín
Campos, Jesús
author_role author
author2 Fernández-Buenestado, Marta
López-Serrano, Joaquín
Campos, Jesús
author2_role author
author
author
dc.contributor.none.fl_str_mv European Commission
Ministerio de Ciencia e Innovación (España)
Agencia Estatal de Investigación (España)
López-Serrano, Joaquín [0000-0003-3999-0155]
Campos, Jesús [0000-0002-5155-1262]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description In the coordination chemistry of heavier tetrylenes (:ER2, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R2P-NR']-, have been barely investigated. Herein, we report the synthesis and structural characterization of such complexes, whose structures drastically differ depending on the group 9 metal precursor used. Strained four-membered {P-N-Ge-M} metallacycles (M = Rh, Ir) are produced from the reaction of phosphinoamido germylenes with [MCl2Cp*]2 precursors (Cp* = η5-C5Me5). At variance, [MCl-(COD)]2 dimers are not broken apart; instead, they afford bimetallic species featuring bridging phosphinoamido-germyl and chloride ligands between the two metals. All new compounds were isolated on a preparative scale and spectroscopically characterized and their structures confirmed by X-ray diffraction. Computational studies support the σ-donor character of the Ge-M interaction and the absence of significant π-backbonding.
publishDate 2025
dc.date.none.fl_str_mv 2025
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/414463
https://api.elsevier.com/content/abstract/scopus_id/105024756264
url http://hdl.handle.net/10261/414463
https://api.elsevier.com/content/abstract/scopus_id/105024756264
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139782NB-I00
Bajo, Sonia; Fernández-Buenestado, Marta; López-Serrano, Joaquín; Campos, Jesús;2025; Supporting Information:Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands; Figshare; https://doi.org/10.1021/acs.organomet.5c00403.s001
Bajo, Sonia; Fernández-Buenestado, Marta; López-Serrano, Joaquín; Campos, Jesús;2025; Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands [Dataset]; Figshare; https://doi.org/10.1021/acs.organomet.5c00403.s002
http://dx.doi.org/10.1021/acs.organomet.5c00403
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
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