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

Yury V. Torubaev, Ivan V. Skabitskiy, Polina Rusina, Alexander A. Pasynskii, Dhirendra K. Rai, Ajeet Singh

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

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.

Original languageEnglish
Pages (from-to)2258-2266
Number of pages9
JournalCrystEngComm
Volume20
Issue number16
DOIs
StatePublished - 1 Jan 2018
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry
  • General Materials Science
  • Condensed Matter Physics

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