An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands

We report the synthesis and characterization of a 24-electron diplatinum(0) complex stabilized by two fluorinated terphenylphos-phonite ligands. This complex features an exceptionally short, unsupported Pt0─Pt 0 bond (2.6348 Å), the shortest structurallyauthenticated to date. Single crystal X-ray di...

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Authors: Alcaide, María M., Álvarez, Eleuterio, López Serrano, Joaquín, Peloso, Riccardo
Format: article
Status:Published version
Publication Date:2026
Country:España
Institution:Universidad de Sevilla (US)
Repository:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:dnet:idus________::58c3296a186b964d48ecf938273f3bf7
Online Access:https://hdl.handle.net/11441/186004
https://doi.org/10.1002/ceur.70287
Access Level:Open access
Keyword:Density functional theory (DFT)
Energy decomposition analysis
Metal–metal bonds
Phosphonite ligands
Platinum complexes
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spelling An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) LigandsAlcaide, María M.Álvarez, EleuterioLópez Serrano, JoaquínPeloso, RiccardoDensity functional theory (DFT)Energy decomposition analysisMetal–metal bondsPhosphonite ligandsPlatinum complexesWe report the synthesis and characterization of a 24-electron diplatinum(0) complex stabilized by two fluorinated terphenylphos-phonite ligands. This complex features an exceptionally short, unsupported Pt0─Pt 0 bond (2.6348 Å), the shortest structurallyauthenticated to date. Single crystal X-ray diffraction reveals a centrosymmetric structure with highly distorted linear coordina-tion and pronounced electronic and coordinative unsaturation. Energy Decomposition (EDA) and Natural Orbital for ChemicalValence (NOCV) Analyses indicate that, while the main attractive component of the Pt─Pt interaction is electrostatic, the orbitalcontribution is also instrumental in the formation of the complex, which is facilitated by the bending of the P–Pt–Pt–P core.Noncovalent Interaction (NCI) and Atoms in Molecules (AIM) analyses support the presence of a Pt─Pt bond and reveal a rolefor the terphenyl substituents of the ligands in the stability of the 24-electrons dimer. Reaction of this species with 1,5-cyclo-octadiene affords a new dinuclear species featuring distorted trigonal planar coordination at each platinum atom. These findingsprovide new insights into metallophilic interactions in closed-shell d10 systems and underscore the ability of bulky phosphoniteligands to stabilize low-coordinate platinum(0) species with unconventional bonding motifs.WileyQuímica InorgánicaMinisterio de Economia, Industria y Competitividad (MINECO). EspañaJunta de AndalucíaAgencia Estatal de Investigación. EspañaEuropean Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)2026info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/186004https://doi.org/10.1002/ceur.70287reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésChemistryEurope, 4 (4), e70287. CTQ2016-75193-PP18-FR-4688info:eu-repo/semantics/openAccessoai:dnet:idus________::58c3296a186b964d48ecf938273f3bf72026-06-17T12:51:07Z
dc.title.none.fl_str_mv An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
title An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
spellingShingle An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
Alcaide, María M.
Density functional theory (DFT)
Energy decomposition analysis
Metal–metal bonds
Phosphonite ligands
Platinum complexes
title_short An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
title_full An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
title_fullStr An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
title_full_unstemmed An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
title_sort An Unusually Short Unsupported Pt─Pt Bond in a 24-Electron Diplatinum(0) Complex With Fluorinated Bis(phosphonite) Ligands
dc.creator.none.fl_str_mv Alcaide, María M.
Álvarez, Eleuterio
López Serrano, Joaquín
Peloso, Riccardo
author Alcaide, María M.
author_facet Alcaide, María M.
Álvarez, Eleuterio
López Serrano, Joaquín
Peloso, Riccardo
author_role author
author2 Álvarez, Eleuterio
López Serrano, Joaquín
Peloso, Riccardo
author2_role author
author
author
dc.contributor.none.fl_str_mv Química Inorgánica
Ministerio de Economia, Industria y Competitividad (MINECO). España
Junta de Andalucía
Agencia Estatal de Investigación. España
European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)
dc.subject.none.fl_str_mv Density functional theory (DFT)
Energy decomposition analysis
Metal–metal bonds
Phosphonite ligands
Platinum complexes
topic Density functional theory (DFT)
Energy decomposition analysis
Metal–metal bonds
Phosphonite ligands
Platinum complexes
description We report the synthesis and characterization of a 24-electron diplatinum(0) complex stabilized by two fluorinated terphenylphos-phonite ligands. This complex features an exceptionally short, unsupported Pt0─Pt 0 bond (2.6348 Å), the shortest structurallyauthenticated to date. Single crystal X-ray diffraction reveals a centrosymmetric structure with highly distorted linear coordina-tion and pronounced electronic and coordinative unsaturation. Energy Decomposition (EDA) and Natural Orbital for ChemicalValence (NOCV) Analyses indicate that, while the main attractive component of the Pt─Pt interaction is electrostatic, the orbitalcontribution is also instrumental in the formation of the complex, which is facilitated by the bending of the P–Pt–Pt–P core.Noncovalent Interaction (NCI) and Atoms in Molecules (AIM) analyses support the presence of a Pt─Pt bond and reveal a rolefor the terphenyl substituents of the ligands in the stability of the 24-electrons dimer. Reaction of this species with 1,5-cyclo-octadiene affords a new dinuclear species featuring distorted trigonal planar coordination at each platinum atom. These findingsprovide new insights into metallophilic interactions in closed-shell d10 systems and underscore the ability of bulky phosphoniteligands to stabilize low-coordinate platinum(0) species with unconventional bonding motifs.
publishDate 2026
dc.date.none.fl_str_mv 2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/186004
https://doi.org/10.1002/ceur.70287
url https://hdl.handle.net/11441/186004
https://doi.org/10.1002/ceur.70287
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ChemistryEurope, 4 (4), e70287.
CTQ2016-75193-P
P18-FR-4688
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812455

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