TY - JOUR

T1 - New look at the Badger-Bauer rule: Correlations of spectroscopic IR and NMR parameters with hydrogen bond energy and geometry. FHF complexes

AU - Тупикина, Елена Юрьевна

AU - Денисов, Глеб Семенович

AU - Меликова, Сона Меджидовна

AU - Кучеров, Сергей

AU - Tolstoy, Peter M.

N1 - Funding Information: This work was financially supported by RFBR grant 17-03-00590 . The calculations were performed in the Computer Center of Saint-Petersburg University Research Park. Appendix A

PY - 2018/7/15

Y1 - 2018/7/15

N2 - In this work correlation dependencies between hydrogen bond energy ΔE for complexes with F–H⋯F hydrogen bond and their spectroscopic characteristics of the IR and NMR spectra are presented. We considered 26 complexes in a wide hydrogen bond energy range 0.2–47 kcal/mol. For each complex we calculated complexation energy (MP2/6-311++G(d,p)), IR spectroscopic parameters (FH stretching frequency ν FH stretching frequency in local mode approximation ν LM at MP2/6-311++G(d,p) level) and NMR parameters (chemical shift of hydrogen δ H and fluorine nuclei δ F, Nuclear Independent Chemical Shielding and spin-spin coupling constants 1J FH, 1hJ H…F, 2hJ FF at B3LYP/pcSseg-2 level). It was shown that changes of parameters upon complexation, i.e. changes of the stretching frequency in local mode approximation Δν LM, change of the proton chemical shift Δδ H and change of the absolute value of spin-spin coupling constant 1J FH could be used for estimation of corresponding hydrogen bond strength. Furthermore, we build correlation dependencies between abovementioned spectroscopic characteristics and geometric ones, such as the asymmetry of bridging proton position q 1 = 0.5·(r FH – r H…F).

AB - In this work correlation dependencies between hydrogen bond energy ΔE for complexes with F–H⋯F hydrogen bond and their spectroscopic characteristics of the IR and NMR spectra are presented. We considered 26 complexes in a wide hydrogen bond energy range 0.2–47 kcal/mol. For each complex we calculated complexation energy (MP2/6-311++G(d,p)), IR spectroscopic parameters (FH stretching frequency ν FH stretching frequency in local mode approximation ν LM at MP2/6-311++G(d,p) level) and NMR parameters (chemical shift of hydrogen δ H and fluorine nuclei δ F, Nuclear Independent Chemical Shielding and spin-spin coupling constants 1J FH, 1hJ H…F, 2hJ FF at B3LYP/pcSseg-2 level). It was shown that changes of parameters upon complexation, i.e. changes of the stretching frequency in local mode approximation Δν LM, change of the proton chemical shift Δδ H and change of the absolute value of spin-spin coupling constant 1J FH could be used for estimation of corresponding hydrogen bond strength. Furthermore, we build correlation dependencies between abovementioned spectroscopic characteristics and geometric ones, such as the asymmetry of bridging proton position q 1 = 0.5·(r FH – r H…F).

KW - Badger-Bauer rule

KW - FHF complexes

KW - Hydrogen bond energy

KW - IR spectroscopy

KW - NMR spectroscopy

KW - Vibrational local mode

KW - POLYATOMIC-MOLECULES

KW - CHEMICAL-SHIFTS

KW - CENTER-DOT-O

KW - DISSOCIATION-ENERGIES

KW - FREQUENCY-SHIFTS

KW - DELTA(5)-3-KETOSTEROID ISOMERASE

KW - PROTON-TRANSFER PATHWAYS

KW - LOCAL MODE MODEL

KW - PHOSPHORYL COMPOUNDS

KW - LOW-TEMPERATURE NMR

UR - http://www.scopus.com/inward/record.url?scp=85044117439&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/new-look-badgerbauer-rule-correlations-spectroscopic-ir-nmr-parameters-hydrogen-bond-energy-geometry

U2 - 10.1016/j.molstruc.2018.03.018

DO - 10.1016/j.molstruc.2018.03.018

M3 - Article

VL - 1164

SP - 129

EP - 136

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

ER -