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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
Author(s) -
Rozhkov Anton V.,
Krykova Mariya A.,
Ivanov Daniil M.,
Novikov Alexander S.,
Sinelshchikova Anna A.,
Volostnykh Marina V.,
Konovalov Mikhail A.,
Grigoriev Mikhail S.,
Gorbunova Yulia G.,
Kukushkin Vadim Yu.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814062
Subject(s) - nucleophile , adduct , chemistry , acetylacetone , crystallography , stereochemistry , metal , catalysis , inorganic chemistry , organic chemistry
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.