Re-evaluation of the bond length-bond strength rule: The stronger bond is not always the shorter bond

A set of 42 molecules with N‐F, O‐F, N‐Cl, P‐F, and As‐F bonds has been investigated in the search for potential bond anomalies, which lead to reverse bond length–bond strength (BLBS) relationships. The intrinsic strength of each bond investigated has been determined by the local stretching force constant obtained at the CCSD(T)/aug‐cc‐pVTZ level of theory. N‐F or O‐F bond anomalies were found for fluoro amine radicals, fluoro amines, and fluoro oxides, respectively. A rationale for the deviation from the normal Badger‐type inverse BLBS relation is given and it is shown that electron withdrawal accompanied by strong orbital contraction and bond shortening is one of the prerequisites for a bond anomaly. In the case of short electron‐rich bonds such as N‐F or O‐F, anomeric delocalization of lone pair electrons in connection with lone pair repulsion are decisive whether a bond anomaly can be observed. This is quantitatively assessed with the help of the CCSD(T) local stretching force constants, CCSD(T) charge distributions, and G4 bond dissociation energies. Bond anomalies are not found for fluoro phosphines and fluoro arsines because the bond weakening effects are no longer decisive. © 2015 Wiley Periodicals, Inc. Reverse bond length/bond strength relations have been reported in the literature, in particular for chemical bonds between electron rich atoms, e.g. NF or OF bonds. In this work, a comprehensive rational is derived covering all electronic and electrostatic factors that may lead to shorter but weaker bonds. A key feature is the use of a qualified bond strength measure based on vibrational spectroscopy.