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Abstract:
Two new trimetallic Cr-Pd hemichelates containing a fluorenyl moiety and two trans arene-bound Cr(CO)(3) moieties were synthesized and fully characterized. Their molecular structures obtained by X-ray diffraction analysis do not show major differences - in interatomic bond lengths within the Pd coordination sphere - when compared to previously reported bimetallic analogues. Theoretical investigations were performed using methods of the Density Functional Theory (ZORA-PBE-D3(BJ)/all electron TZP level, EDA, ETS-NOCV and QTAIM-IQA) to analyse the influence of a second Cr(CO)(3) moiety in the process of formation of the Cr-Pd hemichelate. Theory shows that despite the extensive charge delocalization in the anion of trans-bistricarbonylchromium(fluorene), the formation of a stable hemichelate is still possible albeit requiring a moderate energy payload to funnel charge density towards the formation of the benzylic carbon-palladium bond. IQA analyses of hemichelates show the important role of attractive electrostatic interactions in the dominantly noncovalent Cr(CO)(3)-Pd interactions.
