Issue 16, 2018

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

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

Supplementary files

Article information

Article type
Paper
Submitted
18 dez 2017
Accepted
28 fev 2018
First published
28 fev 2018

CrystEngComm, 2018,20, 2258-2266

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

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