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

Literature Information

Publication Date 2023-10-16
DOI 10.1039/D3CP03714B
Impact Factor 3.676
Authors

E. R. Chakalov, R. P. Shekurov, V. A. Miluykov, P. M. Tolstoy


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Abstract

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.

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DOI: 10.1039/C7CP90253K

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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