Reverse Arene Sandwich Structures Based upon π-Hole⋅⋅⋅[M II ] (d 8 M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

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Abstract

The complexes [Pt(tpp)] (H 2 tpp=tetraphenylporphyrin), [M(acac) 2 ] (M=Pd, Pt, Hacac=acetylacetone), and [Pd(ba) 2 ] (Hba=benzoylacetone) were co-crystallized with highly electron-deficient arene systems to form reverse arene sandwich structures built by π-hole⋅⋅⋅[M II ] (d 8 M=Pt, Pd) interactions. The adduct [Pt(tpp)]⋅2 C 6 F 6 is monomeric, whereas the diketonate 1:1 adducts form columnar infinity 1D-stack assembled by simultaneous action of both π-hole⋅⋅⋅[M II ] and C⋅⋅⋅F interactions. The reverse sandwiches are based on noncovalent interactions and calculated ESP distributions indicate that in π-hole⋅⋅⋅[M II ] contacts, [M II ] plays the role of a nucleophile.

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Rozhkov, A. V., Krykova, M. A., Ivanov, D. M., Novikov, A. S., Sinelshchikova, A. A., Volostnykh, M. V., … Kukushkin, V. Y. (2019). Reverse Arene Sandwich Structures Based upon π-Hole⋅⋅⋅[M II ] (d 8 M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile. Angewandte Chemie - International Edition, 58(13), 4164–4168. https://doi.org/10.1002/anie.201814062

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