TY - JOUR
T1 - 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
AU - Olea Ulloa, Carolina
AU - Attia, Amr A.A.
AU - Lupan, Alexandru
AU - King, R. Bruce
AU - Muñoz-Castro, Alvaro
N1 - Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2024/1
Y1 - 2024/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85177165206&partnerID=8YFLogxK
U2 - 10.1016/j.inoche.2023.111680
DO - 10.1016/j.inoche.2023.111680
M3 - Article
AN - SCOPUS:85177165206
SN - 1387-7003
VL - 159
JO - Inorganic Chemistry Communication
JF - Inorganic Chemistry Communication
M1 - 111680
ER -