Reverse Arene Sandwich Structures Based upon π-Hole⋅⋅⋅[MII ] (d8 M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

Anton V Rozhkov; Mariya A Krykova; Daniil M Ivanov; Alexander S Novikov; Anna A Sinelshchikova; Marina V Volostnykh; Mikhail A Konovalov; Mikhail S Grigoriev; Yulia G Gorbunova; Vadim Yu Kukushkin

doi:10.1002/anie.201814062

Reverse Arene Sandwich Structures Based upon π-Hole⋅⋅⋅[M^II ] (d⁸ M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

Angew Chem Int Ed Engl. 2019 Mar 22;58(13):4164-4168. doi: 10.1002/anie.201814062. Epub 2019 Feb 14.

Affiliations

¹ Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034, Saint Petersburg, Russian Federation.
² Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky Pr. 31-4, 119071, Moscow, Russian Federation.

PMID: 30667579
DOI: 10.1002/anie.201814062

Abstract

The complexes [Pt(tpp)] (H₂ 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 ] (d⁸ M=Pt, Pd) interactions. The adduct [Pt(tpp)]⋅2 C₆ F₆ 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.

Keywords: noncovalent interactions; palladium; platinum; reverse sandwich complexes; π-hole interactions.

Reverse Arene Sandwich Structures Based upon π-Hole⋅⋅⋅[M^II ] (d⁸ M=Pt, Pd) Interactions, where Positively Charged Metal Centers Play the Role of a Nucleophile

Authors

Affiliations

Abstract

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