Unraveling Unsupported Gold···Platinum Metallophilic Interactions: An In-Depth Computational and Topological Study
Félix Reboiro1, Daniel Blasco1, M Elena Olmos1
1Departamento de Química, Instituto de Investigación en Química, Complejo Científico Tecnológico, Universidad de La Rioja, Madre de Dios 53, 26006 Logroño, La Rioja, Spain.
Abstract:
We have computationally studied the attraction between gold and platinum atoms in a series of unsupported model systems with formulas cis/trans-[Pt(CH3)2(NH3)2][Au(CH3)3(NH3)] (1a/1b), cis/trans-[Pt(CH3)2(NH3)2][Au(CH3)(NH3)] (2a/2b), [Pt(CH3)(NH3)3][Au(CH3)2] (3), and {[Pt(NH3)4][Au(CH3)2]}+ (4). These systems stem from the simplification of the well-known orthometalated complexes of these metals, allowing for a clearer-as-possible description of the metallophilic interaction while reducing computation cost and keeping chemical representativeness. To achieve this goal, we fully optimized the model systems at the MP2 level of theory with the def2-TZVP basis sets. We analyzed the interaction energy at equilibrium distances through potential energy curves at the RHF and MP2 levels of theory, employing different relativistic pseudopotentials. Additionally, we examined various parameters, including natural bonding orbital effective charges or bond orders, and conducted an in-depth topological analysis of the electron density. The Au···Pt interaction has been characterized as a regular closed-shell interaction with some degree of electron sharing, but weaker (ca. 15 kJ·mol-1) than other metallophilic interactions, such as Au···Au or Au···Hg. Overall, this study sheds light on the key factors influencing the Au···Pt interaction.
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