Competing intramolecular vs. intermolecular hydrogen bonding in phosphoryl-containing secondary alkanols: A structural, spectroscopic and DFT study

Intramolecular hydrogen bonding competes with intermolecular hydrogen bonding in alkanols containing Ph2P(O) group. A character of H-bonding in secondary alkanols Ph2P(O) (CR2)nCH2CH(OH)Me, where n = 0 (1), n = 1, R = H (2), and n = 1, R = Me (3) in crystal state and solutions has been studied by X-ray diffraction, FTIR, and diffusion ordered NMR spectroscopy (DOSY). Quantum chemical calculations and QTAIM analysis of isolated alkanol molecules and their dimers have been performed. In spite of slight difference in the structure of linker between P(O) and OH groups, the studied alcohols in crystal exhibit three types of H-bonds: dimer with intermolecular H-bond, polymeric chains with intermolecular H-bond, and monomer with intramolecular H-bond. Experimental data agree well with structural data of quantum chemical calculations at the M06-2x/6-311G (d,p) level of theory. Energy values (thermodynamic parameters) of DFT-optimized structures for gauche and anti isomers and dimers have been calculated. According to FTIR data in solutions (0.1–0.0001 M), alcohol 1 is the most associated, association of alcohol 2 is much less expressed, while alcohol 3 remains as H-bound monomer. Particle size assessed by DOSY relative to Ph3CH does not change on dilution for alcohols 2 and 3 but varies for alcohol 1. © 2018 Elsevier B.V.

Authors
Pasechnik M.P.1 , Matveeva A.G.1 , Lyssenko K.A.1 , Aysin R.R. 1 , Smol'yakov A.F. 1, 2 , Zubavichus Y.V. 3 , Godovikov I.A.1 , Goryunov E.I.1
Language
English
Pages
874-881
Status
Published
Volume
1175
Year
2019
Organizations
  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St, Moscow, 119991, Russian Federation
  • 2 Faculty of Science, RUDN University, 6 Miklukho-Maklaya St, Moscow, 117198, Russian Federation
  • 3 National Research Center “Kurchatov Institute”, pl. Akad. Kurchatova, 1, Moscow, 123098, Russian Federation
Keywords
DFT calculations; FTIR spectroscopy; Hydrogen bonding; Secondary P,P-diphenylphosphorylalkanols; Solutions; X-ray diffraction
Date of creation
04.02.2019
Date of change
04.02.2019
Short link
https://repository.rudn.ru/en/records/article/record/36097/
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