Halogen Bonding with Dihalogens and Interhalogens - Halogen Bonding: Fundamentals and Applications - page 64

Halogen Bonding with Dihalogens and Interhalogens

William T. Pennington 1 ( )·TimothyW.Hanks 2 · Hadi D. Arman 1

1 Department of Chemistry, Hunter Chemistry Laboratory,
Clemson University, Clemson, SC 29634-1905, USA
[e-mail]
2 Department of Chemistry, Furman University, Greenville, SC 29613, USA

1 I tr cti n ................................... 66

1.1 HistoricalBackground ............................. 66

1.2 SignificanceofHalogenBondingwithDihalogens .............. 68

2 Crystal Structures ................................ 69

2.1 GeneralObservations .............................. 69

2.2 NitrogenandOxygenElectronDonors .................... 87

2.3 PhosphorusandSulfurElectronDonors ................... 88

2.4 ArsenicandSeleniumElectronDonors .................... 89

3 Computation Studies .............................. 90

3.1 GeneralObservations .............................. 90

3.2 OxygenElectronDonors ............................ 92

3.3 NitrogenElectronDonors ........................... 93

3.4 SulfurandSeleniumElectronDonors..................... 95

3.5 π -ElectronDonors ............................... 97

References ....................................... 98

Abstract The fact that iodine forms complexes with Lewis bases has been recognized
since at least the middle of the nineteenth century. With the development of X-ray crys-
tallography and modern spectroscopic techniques, the directionality and strength of
halogen bonds has been determined. Halogen bonds between dihalogens and Lewis bases
fall into four main categories: simple adducts, bridging adducts, amphoteric adducts, and
adducts that are both bridging and amphoteric. In the case of very strong interactions
between the electron donor and the dihalogen, the halogen-halogen bond is broken, lead-
ing to ionic or oxidative addition products. The theoretical description of the halogen
bond has also progressed, in parallel with the development of increasingly sophisticated
theories of bonding. Relatively accurate predictions of structural parameters and interac-
tion energies are now possible, but they present a challenge to available computational
hardware and software.

Keywords Halogen bond · Crystallography · Molecular modeling · ab initio ·

Charge transfer

Abbreviations
BSSE Basis set superposition error

DFT Density functional theory