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

The effects on the C-I⋅⋅N halogen bond between iodobenzene and NH 3 of placing various substituents on the phenyl ring are monitored by quantum calculations. Substituents R=N(CH 3 ) 2 , NH 2 , CH 3 , OCH 3 , COCH 3 , Cl, F, COH, CN, and NO 2 were each placed ortho, meta, and para to the I. The depth of the σ-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⋅⋅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.