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“Bottled” spiro-doubly aromatic trinuclear [Pd2Ru]+ complexes
Authors:Maksim Kulichenko,Nikita Fedik,Anna Monfredini,Alvaro Muñ  oz-Castro,Davide Balestri,Alexander I. Boldyrev,Giovanni Maestri
Affiliation:Department of Chemistry and Biochemistry, Utah State University, Logan UT 84322 USA.; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma, Parco Area delle Scienze 17/A, 43124 Parma Italy ; Grupo de Química Inorgánica y Materiales Moleculares, Facultad de Ingeniería, Universidad Autonoma de Chile, El Llano Subercaseaux 2801, Santiago Chile
Abstract:Following an ongoing interest in the study of transition metal complexes with exotic bonding networks, we report herein the synthesis of a family of heterobimetallic triangular clusters involving Ru and Pd atoms. These are the first examples of trinuclear complexes combining these nuclei. Structural and bonding analyses revealed both analogies and unexpected differences for these [Pd2Ru]+ complexes compared to their parent [Pd3]+ peers. Noticeably, participation of the Ru atom in the π-aromaticity of the coordinated benzene ring makes the synthesized compound the second reported example of ‘bottled’ double aromaticity. This can also be referred to as spiroaromaticity due to the participation of Ru in two aromatic systems at a time. Moreover, the [Pd2Ru]+ kernel exhibits unprecedented orbital overlap of Ru dz2 AO and two Pd dxy or dx2y2 AOs. The present findings reveal the possibility of synthesizing stable clusters with delocalized metal–metal bonding from the combination of non-adjacent elements of the periodic table which has not been reported previously.

Synthesis of a triangular [Pd2Ru]+ complex with delocalized metal–metal bonding between non-adjacent elements of the periodic table, double aromaticity and overlap of d-AOs with different angular momentum.
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