Quantum Chemical Dissection of the Shortest P=O⋅⋅⋅I Halogen Bond: The Decisive Role of Crystal Packing Effects

Tobias A Schaub; Rebecca Sure; Frank Hampel; Stefan Grimme; Milan Kivala

doi:10.1002/chem.201701234

Quantum Chemical Dissection of the Shortest P=O⋅⋅⋅I Halogen Bond: The Decisive Role of Crystal Packing Effects

Chemistry. 2017 Apr 27;23(24):5687-5691. doi: 10.1002/chem.201701234. Epub 2017 Apr 11.

Authors

Tobias A Schaub¹, Rebecca Sure², Frank Hampel¹, Stefan Grimme², Milan Kivala¹

Affiliations

¹ Department of Chemistry and Pharmacy, Chair of Organic Chemistry I, University of Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
² Mulliken Center for Theoretical Chemistry, Institute for Physical and Theoretical Chemistry, Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.

PMID: 28324621
DOI: 10.1002/chem.201701234

Abstract

A supramolecular arrangement comprising a bridged triarylphoshine oxide and an aryl iodide is reported, featuring the shortest ever reported P=O⋅⋅⋅I halogen bond of 2.683(5) Å in the solid state. X-ray crystallographic analysis together with modern quantum chemical methods were enlisted to dissect the individual contributions that compelled this exceptionally short halogen bond, pointing out the decisive role of crystal packing effects.

Keywords: X-ray diffraction; density functional calculations; halogen bonding; phosphorus heterocycles; supramolecular chemistry.