Jump to main content
Jump to site search

Issue 16, 2018
Previous Article Next Article

Organometallic halogen bond acceptors: directionality, hybrid cocrystal precipitation, and blueshifted CO ligand vibrational band

Author affiliations

Abstract

Iron cyclopentadienyl carbonyl-halide and -chalcogenolate complexes CpFe(CO)2X (X = Cl, Br, I, TePh, SPh) readily afford cocrystals with the bidentate halogen bond donor 1,4-diiodotetrafluorobenzene (p-DITFB) under slow evaporation or vapor diffusion conditions. The same microcrystalline [CpFe(CO)2TePh](p-DITFB) product instantly precipitates upon mixing p-DITFB and CpFe(CO)2TePh in hexane solution. Supramolecular [CpFe(CO)2X(p-DITFB)]n chains in the cocrystals are assembled by halogen bonds (XB) between the electrophilic area of iodine atoms of p-DITFB and the nucleophilic area of X in CpFe(CO)nX. The 5–10 cm−1 hypsochromic shift of the CO stretching bands in the IR spectra of [CpFe(CO)2X(p-DITFB)] cocrystals is explained by the pronounced electron-withdrawing effect of halogen bonding (XB), as supported by DFT calculations. The observed influence of the nature of the XB acceptor (X) on the XB geometry is described in terms of hybridization and electrostatic surface potential (ESP) mapping.

Graphical abstract: Organometallic halogen bond acceptors: directionality, hybrid cocrystal precipitation, and blueshifted CO ligand vibrational band

Back to tab navigation

Supplementary files

Publication details

The article was received on 18 Dec 2017, accepted on 28 Feb 2018 and first published on 28 Feb 2018


Article type: Paper
DOI: 10.1039/C7CE02185B
Citation: CrystEngComm, 2018,20, 2258-2266
  •   Request permissions

    Organometallic halogen bond acceptors: directionality, hybrid cocrystal precipitation, and blueshifted CO ligand vibrational band

    Y. V. Torubaev, I. V. Skabitskiy, P. Rusina, A. A. Pasynskii, D. K. Rai and A. Singh, CrystEngComm, 2018, 20, 2258
    DOI: 10.1039/C7CE02185B

Search articles by author

Spotlight

Advertisements