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...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2026 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:dnet:idus________::58c3296a186b964d48ecf938273f3bf7 |
| Acceso en línea: | https://hdl.handle.net/11441/186004 https://doi.org/10.1002/ceur.70287 |
| Access Level: | acceso abierto |
| Palabra clave: | Density functional theory (DFT) Energy decomposition analysis Metal–metal bonds Phosphonite ligands Platinum complexes |
| Sumario: | 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. |
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