| dc.description | 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. | |
