Influence of Substituents in the Benzene Ring on the Halogen Bond of Iodobenzene with Ammonia

The effects on the C-I center dot center dot N halogen bond between iodobenzene and NH3 of placing various substituents on the phenyl ring are monitored by quantum calculations. Substituents R=N(CH3)(2), NH2, CH3, OCH3, COCH3, Cl, F, COH, CN, and NO2 were each placed ortho, meta, and para to the I. The depth of the sigma-hole on I is deepened as R becomes more electron-withdrawing which is reflected in a strengthening of the halogen bond, which varied between 3.3 and 5.5 kcal mol(-1). In most cases, the ortho placement yields the largest perturbation, followed by meta and then para, but this trend is not universal. Parallel to these substituent effects is a progressive lengthening of the covalent C-I bond. Formation of the halogen bond reduces the NMR chemical shielding of all three nuclei directly involved in the C-I center dot center dot N interaction. The deshielding of the electron donor N is most closely correlated with the strength of the bond, as is the coupling constant between I and N, so both have potential use as spectroscopic measures of halogen bond strength.