In:
Inorganic Chemistry Frontiers, Royal Society of Chemistry (RSC), Vol. 8, No. 23 ( 2021), p. 4965-4975
Abstract:
Cocrystallization of the palladium acetate cluster Pd 3 (OAc) 6 (abbreviated as [Pd 3 ]) with electron-deficient iodine( i )-based perfluoroarenes (Ar F I: iodopentafluorobenzene, 4-iodoheptafluorotoluene, 1,4-diiodotetrafluorobenzene, 1,2-diiodotetrafluorobenzene, and octafluoro-4,4′-diiodo-1,1-biphenyl) and iodine-free octafluoronaphthalene gave a series of six cocrystals [Pd 3 ]·(arene) studied by single-crystal X-ray diffractometry. Significant intermolecular noncovalent interactions were verified by a density functional theory study, molecular electrostatic potential and Hirshfeld surface analyses, a combined QTAIM/NCPlot approach, and NBO and energy framework calculations. In five out of six structures, the aromatic rings coupled with cluster [Pd 3 ] via lone pair–π-(Ar F )-hole interactions. The iodine-containing arenes, Ar F I, were additionally involved in halogen bonding with carboxylate O centers, but inorganic–organic stacking still remained the structure-determining interaction. In the stacking, the electron-rich PdO 4 plane behaved as a five-center nucleophile providing oxygen lone pairs in addition to the d z 2 -Pd II orbital; this plane complemented the π-acidic surface of the arenes, affording highly polar circular stacking, where organics wrapped inorganics.
Type of Medium:
Online Resource
ISSN:
2052-1553
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2021
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