Halogen Bonding and CO-Ligand Blue-Shift in Hybrid Organic—Organometallic Cocrystals [CpFe(CO)2X] (C2I4) (X = Cl, Br)

This work is focused on the complex interplay of geometry of I· · · X halogen bonds (HaB) and intermolecular interaction energy in two isomorphic cocrystals [CpFe(CO)2X] (C2 I4 ) (X = Cl (1), Br (2)). Their IR-spectroscopic measurements in solid state and solution demonstrate the blue-shift of CO vibration bands, resulting from I· · · X HaB. The reluctance of their iodide congener [CpFe(CO)2 I] to form the expected cocrystal [CpFe(CO)2 I] (C2 I4 ) is discussed in terms of different molecular electrostatic potential (MEP) of the surface of iodide ligands, as compared with chloride and bromide, which dictate a different angular geometry of HaB around the metal-I and metal-Br/Cl HaB acceptors. This study also suggests C2 I4 as a reliable HaB donor coformer for metal-halide HaB acceptors in the crystal engineering of hybrid metal–organic systems. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

Authors
Torubaev Y.1 , Skabitskiy I.1 , Shapovalov S.1 , Tikhonova O.1 , Popova A. 2
Journal
Publisher
MDPI AG
Number of issue
3
Language
English
Status
Published
Number
412
Volume
12
Year
2022
Organizations
  • 1 Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russian Federation
  • 2 The Faculty of Physics, Mathematics and Natural Sciences, Peoples’ Friendship University of Russia (RUDN), Moscow, 117198, Russian Federation
Keywords
blue-shift; cocrystal; halogen bonding; σ-hole
Date of creation
06.07.2022
Date of change
06.07.2022
Short link
https://repository.rudn.ru/en/records/article/record/83786/
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