Evidence of extremely short hydrogen bond in the homoconjugated ferrocene-1,1'-diyl-bisphosphinic acid anion: sign change of the H/D isotope effect on the 31P NMR chemical shift.

The structure of the two intramolecular hydrogen-bonded motifs within ferrocene-1,1'-diyl-bisphosphinic acid, a cyclic dimer and a homoconjugated anion, has been experimentally revealed by NMR spectroscopy for a solution in a low-freezing polar aprotic CDF3/CDF2Cl medium at 100 K. Structure elucidation was achieved with the help of the H/D isotope effects on the 1H, 2H and, for the first time, 31P NMR chemical shifts. The questions of bridging hydron localization and origins of opposite signs of H/D isotope effects on the 31P NMR chemical shifts in the cyclic dimer and homoconjugated anion have also been addressed by DFT calculations, including numerical solution of the Schrödinger equation for proton and deuteron vibrations in the anharmonic double well potentials.

Estimations of OH·N hydrogen bond length from positions and intensities of IR bands.

In this computational work applicability of IR spectral parameters for evaluations of OH···N hydrogen bond length is discussed. For a set of 124 complexes with OH···N hydrogen bond formed by combinations of methanol/acetic acid and pyridine (and their fluorine substituted versions) geometries, energies and IR parameters were calculated at MP2/def2-TZVP level of theory. For a number of IR parameters (the shift of proton donor group stretching vibration Δνs, increase of its intensity I, the low-frequency hydrogen bond stretching vibration νσ, bending in-plane δ and out-of-plane γ vibrations) equations linking them with interatomic distances are proposed, the robustness and accuracy of such equations are discussed. The enthalpy of OH···N hydrogen bond formation ΔH was also linked with electron density parameters in (3; -1) critical point.