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The Study of Molecular Dynamics by NMR Spectroscopy

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (15 April 2021) | Viewed by 3538

Special Issue Editor


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Guest Editor
David Ellis, Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot‐Watt University, Edinburgh EH14 4AS, UK
Interests: NMR spectroscopy; applications of NMR to the study of molecular dynamics in solution; fluxionality in organometallics and boron clusters; NMR spectroscopy of complex mixtures

Special Issue Information

Dear Colleagues,

In 1945, Purcell and Bloch, working independently, and within a few weeks of each other, first observed the property of nuclear magnetic resonance in condensed matter. In 1952, they were jointly awarded the Nobel Prize for Physics for their work. We have come a long way since then. Now, in 2020, NMR is considered to be a vital tool in chemical analysis, a workhorse for identifying unknown compounds. However, NMR is much more than that, finding wide applications across the physical and biological sciences. It supports pharmaceutical and other medical endeavours, including MRI; and, it contributes to studies in materials chemistry through solid-state NMR, the latter being used to study such diverse topics as conduction in batteries and the degradation of peat. Interest is increasing in how NMR, in combination with metabonomics and other forms of data analysis, may be able to assist in authentication of high-value products, and the list continues to grow. In this Special Issue, we focus on applications of NMR in the study of molecular dynamics in solution, in the widest sense. Many organic, organometallic, and coordination compounds display fluxional behaviour, NMR having played a major role over many years in the elucidation of mechanistic information, kinetics, and thermodynamics. We invite contributions from those working in the field of molecular dynamics as studied by NMR in either solid-state or in solution.

Dr. David Ellis
Guest Editor

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Keywords

  • NMR spectroscopy
  • Fluxionality
  • Molecular Dynamics
  • Variable temperature NMR
  • Organometallic chemistry
  • Clusters
  • Thermodynamics
  • Simulation
  • Kinetics
  • Mechanistic studies
  • Inversion
  • Exchange spectroscopy
  • Chemical exchange
  • Multi-dimensional NMR techniques

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Published Papers (1 paper)

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14 pages, 2732 KiB  
Article
Benchmarking the Fluxional Processes of Organometallic Piano-Stool Complexes
by Nathan C. Frey, Eric Van Dornshuld and Charles Edwin Webster
Molecules 2021, 26(8), 2310; https://doi.org/10.3390/molecules26082310 - 16 Apr 2021
Cited by 3 | Viewed by 3005
Abstract
The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M [...] Read more.
The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)3 were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)3 complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)3 were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)3. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d′); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol−1. Notably, PBE0/BS1 describes the (CO)3 rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)3 complexes (except for (TMCOT)W(CO)3), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)3 complex (computed with the PBE0 functional) has a ΔG of 12.6, 12.8, and 13.2 kcal mol−1 for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed 1H-NMR and 13C-NMR chemical shifts for (TMCOT)Cr(CO)3 and (TMCOT)Mo(CO)3 at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures. Full article
(This article belongs to the Special Issue The Study of Molecular Dynamics by NMR Spectroscopy)
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