Difluorobenzenes revisited: an experimental and theoretical study of spin-spin coupling constants for 1,2-, 1,3-, and 1,4-difluorobenzene

The experimental spin–spin coupling constants (SSCCs) for 1,3‐ and 1,4‐difluorobenzene have been determined anew, and found to be consistent with previously determined values. SSCCs for 1,2‐, 1,3‐, and 1,4‐difluorobenzene have been analyzed by comparing them with the coupling constants computed usin...

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Bibliographic Details
Published in:Magnetic resonance in chemistry 2010-01, Vol.48 (1), p.68-73
Main Authors: Alkorta, Ibon, Blanco, Fernando, Del Bene, Janet E., Elguero, José, Hernández-Folgado, Laura, Jimeno, María-Luisa
Format: Article
Language:English
Subjects:
13C
19F
Approximation
Clusters
Computation
Computer Simulation
Constants
difluorobenzenes
Empirical equations
EOM-CCSD
Fluorobenzenes - chemistry
Joining
Mathematical analysis
Molecular Structure
SOPPA
Spin-spin coupling
SSCCs
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Summary:The experimental spin–spin coupling constants (SSCCs) for 1,3‐ and 1,4‐difluorobenzene have been determined anew, and found to be consistent with previously determined values. SSCCs for 1,2‐, 1,3‐, and 1,4‐difluorobenzene have been analyzed by comparing them with the coupling constants computed using the second‐order polarization propagator approximation (SOPPA) and the equation‐of‐motion coupled cluster singles and doubles method (EOM‐CCSD). Eighty experimental values have been analyzed using SOPPA calculations, and a subset of 40 values using both SOPPA and EOM‐CCSD approaches. One‐bond coupling constants 1J(CC) and 1J(CF) are better described by EOM‐CCSD, whereas one‐bond 1J(CH) values are better described by SOPPA. An empirical equation is presented which allows for the prediction of unknown coupling constants from computed SOPPA values. A similar approach may prove useful for predicting coupling constants in larger systems. Copyright © 2009 John Wiley & Sons, Ltd. Spin‐spin coupling constants (SSCCs) of 1,2‐, 1,3‐, and 1,4‐difluorobenzene have been analyzed by comparison with computed SOPPA and EOM‐CCSD coupling constants. Eighty experimental values have been analyzed using SOPPA calculations, and a subset of 40 values using both SOPPA and EOM‐CCSD approaches. One‐bond coupling constants 1J(C‐C) and 1J(C‐F) are better described at EOM‐CCSD, while one‐bond 1J(C‐H) values are better described at SOPPA. An empirical equation is presented which allows for the prediction of unknown coupling constants from computed SOPPA values.
ISSN:0749-1581
1097-458X
1097-458X
DOI:10.1002/mrc.2543