Resolving an apparent discrepancy between theory and experiment: spin–spin coupling constants for FCCF

Bene, Janet E. Del; Provasi, Patricio F.; Alkorta, Ibón; Elguero, José

doi:10.1002/mrc.2304

Cited by 27 publications

(21 citation statements)

References 31 publications

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“…6 In 1968, this author reported the remarkable basicity of 1,8-bis(dimethylamino)naphthalene (DMAN), trademarked by Aldrich as Proton Sponge. super basicity, 7-11 vibrational spectrum, 12 including theoretical 13 NMR spectroscopy (chemical shifts and spin-spin coupling constants), [14][15][16][17][18] and experimental X-ray diffraction studies. super basicity, 7-11 vibrational spectrum, 12 including theoretical 13 NMR spectroscopy (chemical shifts and spin-spin coupling constants), [14][15][16][17][18] and experimental X-ray diffraction studies.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Sánchez‐Sanz

Trujillo

Alkorta

et al. 2014

Phys. Chem. Chem. Phys.

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A computational study of the intramolecular pnicogen bond in 1,8-bis-substituted naphthalene derivatives (ZXH and ZX2 with Z = P, As and X = H, F, Cl, and Br), structurally related to proton sponges, has been carried out. The aim of this paper is the study of their structural parameters, interaction energies and electronic properties such as electron density on the intramolecular interaction. The calculated geometrical parameters associated to the P···P interaction are in reasonably good agreement with the crystal structures found in a CSD search, in particular those of the halogen derivatives. Isodesmic reactions where the 1,8-bis-substituted derivatives are compared to monosubstituted derivatives have been calculated, indicating that the 1,8 derivatives are more stable than the monosubstituted ones for those cases with X-Z···Z-X and F-Z···Z-H alignments. Electron densities and Laplacians at the BCP on the pnicogen interactions suggest that they can be classified as pure closed shell interactions with a partial covalent character. Electron density shift maps are consistent with the results for intermolecular pnicogen interactions. Relationships between interatomic distance and electron density at the bond critical points and between interatomic distance and the orbital charge transfer stabilization energies have been found.

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Section: Introductionmentioning

confidence: 99%

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Sánchez‐Sanz

Trujillo

Alkorta

et al. 2014

Phys. Chem. Chem. Phys.

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“…22 Although the importance of zero-point vibrational corrections has been demonstrated previously by others, imposing such corrections does not always lead to better agreement with experiment. For example, in a previous study of FCCF, 18 we demonstrated that the three-bond F-F coupling constant was extremely sensitive to geometry. Optimized geometries even at CCSD(T)/aug-cc-pVTZ had C-C and C-F distances that were too long and absolute values of 3 J(F-F) which were significantly greater than the experimental value of this coupling constant.…”

Section: Methodsmentioning

confidence: 91%

Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin−Spin Coupling Constants for Molecules with C, N, and O Double and Triple Bonds and Selected F-Substituted Derivatives

Bene

Alkorta

Elguero

2008

J. Chem. Theory Comput.

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Ab initio EOM-CCSD and SOPPA calculations with the Ahlrichs (qzp,qz2p) basis set have been carried out to evaluate one-, two-, and three-bond spin-spin coupling constants for molecules HmXYHn and HmXYHn for X, Y = (13)C, (15)N, and (17)O, and selected (19)F-substituted derivatives. In the great majority of cases, EOM-CCSD one-bond C-C, C-N, C-O, C-F, N-N, N-O, and N-F coupling constants and three-bond F-F coupling constants are smaller in absolute value than the corresponding SOPPA coupling constants, with the EOM-CCSD values in better agreement with experimental data. SOPPA tends to significantly overestimate the absolute values of large one- and three-bond couplings involving fluorine. The majority of two-bond SOPPA coupling constants are in better agreement with experiment than EOM-CCSD, although differences between EOM-CCSD and experimental values are not dramatic. A statistical analysis of thirty EOM-CCSD and SOPPA coupling constants versus experimental coupling constants demonstrates that better agreement with experiment is found when EOM-CCSD is the computational method.

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“…The EOM-CCSD method with the Ahlrichs (qzp,qz2p) basis set has been shown to yield coupling constants in good agreement with experimental values for molecules. [19][20][21][22] Its application to hydrogen-bonded complexes has provided insight into experimentally determined coupling constants, 23 and the predicted relationship between 2h J(N-N) and the N-N distance for N-HÁÁÁN hydrogen bonds 24 has been verified experimentally. 25 Finally, the computed signs and magnitudes of 2h J(X-Y), 1h J(H-Y), and 1 J(X-H) for X-HÁÁÁY hydrogen bonds have been used successfully to characterize hydrogen-bond type.…”

Section: Methodsmentioning

confidence: 92%

Do corresponding coupling constants in hydrogen-bonded homo- and hetero-chiral dimers differ?

2010

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Ab initio equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations have been carried out to evaluate spin-spin coupling constants in six pairs of homo-and hetero-chiral dimers: (HOOH) 2 , (H 2 NNH 2 ) 2 , (FOOH) 2 , (FHNNH 2 ) 2 , (HOOOH) 2 , and (FOOOH) 2 . Corresponding spin-spin coupling constants in these isomeric pairs of C2 and Ci symmetry may differ, but these differences are small and may not be detectable experimentally. For the complexes with O1-HÁÁÁO and O1-HÁÁÁF hydrogen bonds, 1 J(O1-H) has a larger absolute value in the C2 isomer. For the same set of complexes, 1 J(O1-O2) has a larger absolute value in the Ci isomer. No distinguishable patterns could be discerned in the remaining spin-spin coupling constants in the C2 and Ci isomers of these complexes, nor in complexes with N-HÁÁÁN hydrogen bonds. Résumé: Des calculs ab initio EOM-CCSD ont été effectués pour évaluer les constantes de couplage spin-spin dans six paires de dimères homo-et heterochiral : (HOOH)2, (H2NNH2)2, (FOOH)2, (FHNNH2)2, (HOOOH)2, et (FOOOH)2. Les correspondantes constantes de couplage spin-spin dans les paires d'isomères sont, en général, différentes mais les différen-ces sont faibles au point, pour certaines d'entre elles, de ne pas pouvoir être détectées expérimentalement. Pour les complexes avec des liaisons hydrogène O-HÁÁÁO et O-HÁÁÁF, 1 J(O1-H) a une plus large valeur absolue dans l'isomère C2. Pour le même ensemble des complexes, 1 J(O1-O2) a une plus large valeur absolue dans l'isomère Ci. On ne trouve pas des rè-gles générales pour les restantes constantes de couplage spin-spin dans les isomères C2 et Ci de ces complexes et non plus dans les complexes avec des liaisons hydrogène N-HÁÁÁN. Mots-clés : constantes de couplage spin-spin, homo-et hetero-chiral dimères, liaisons hydrogène.

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Resolving an apparent discrepancy between theory and experiment: spin–spin coupling constants for FCCF

Cited by 27 publications

References 31 publications

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Intramolecular pnicogen interactions in phosphorus and arsenic analogues of proton sponges

Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin−Spin Coupling Constants for Molecules with C, N, and O Double and Triple Bonds and Selected F-Substituted Derivatives

Do corresponding coupling constants in hydrogen-bonded homo- and hetero-chiral dimers differ?

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