Mostrar el registro sencillo del ítem
Dual spherical-spherical aromaticity in [M(η2-P4)2]+ (M = Cu, Ag, Au) and [P(P4)2]+. Evaluation of bonding nature and spherical aromatic character of the P4 aggregates from DFT calculations
dc.contributor.author | Olea Ulloa, Carolina | |
dc.contributor.author | Attia, Amr A.A. | |
dc.contributor.author | Lupan, Alexandru | |
dc.contributor.author | King, R. Bruce | |
dc.contributor.author | Muñoz-Castro, Alvaro | |
dc.date.accessioned | 2024-06-19T05:01:02Z | |
dc.date.available | 2024-06-19T05:01:02Z | |
dc.date.issued | 2024 | |
dc.identifier | 10.1016/j.inoche.2023.111680 | |
dc.identifier.issn | 13877003 | |
dc.identifier.uri | https://hdl.handle.net/20.500.12728/11428 | |
dc.description.abstract | The favorable coordination of two P4 units to a coinage metal center, given by [M(η2–P4)2]+ and [P(P4)2]+ clusters, offers an interesting template for evaluating how two spherical aromatic units interact when bridged by either a metal or a main-group element center. Our results indicate a M+–(P4)2 stabilization trend in the order Au > Cu > Ag, involving mainly electrostatic character, followed by a sizable contribution from covalent (orbital) character, with a slight London dispersion type stabilization. The coordination scheme is based on a σ- M+←(η2-P4)2 charge transfer, followed by σ-metal-to-ligand backbonding, in addition to a set of two σ-ligand-to-metal and π-ligand-to-metal charge transfer bonds. Such structural features bring together two spherical aromatic P4 units, leading to the formation of a dual aromatic cluster mediated by a coinage metal center, i.e. two independent aromatic units within the same cluster. However, in [P(P4)2]+ involving stronger covalent P4–P bonds, the spherical aromatic character decreases, owing to the larger distortion of the P4 units, as result of the larger bonding interaction towards the central P atom. Hence, the coordination towards a coinage metal center of the P4 unit incorporates multiple aromatic units into a single molecular entity. This provides a model to envisage larger connected spherical-aromatic species serving as building blocks while retaining their inherent characteristics. © 2023 Elsevier B.V. | es_ES |
dc.description.sponsorship | Fondo Nacional de Desarrollo Científico y Tecnológico, FONDECYT, (1221676) | es_ES |
dc.language.iso | en | es_ES |
dc.publisher | Elsevier B.V. | es_ES |
dc.title | Dual spherical-spherical aromaticity in [M(η2-P4)2]+ (M = Cu, Ag, Au) and [P(P4)2]+. Evaluation of bonding nature and spherical aromatic character of the P4 aggregates from DFT calculations | es_ES |
dc.type | Article | es_ES |