Nuclear spin-spin coupling via nonbonded interactions. 8. The distance dependence of through-space fluorine-Fluorine coupling

Journal of the American Chemical Society

Volumn 122, Issue 17, 2000, Pages 4108-4116

  Mallory, Frank B ^a   Mallory, Clelia W ^b   Butler, Kelly E ^a   Lewis, Mary Beth ^a   Xia, Angell Qian ^a   Luzik Jr , Eddie D ^a   Fredenburgh, Laura E ^a   Ramanjulu, Mercy M ^a   Van, Que N ^a   Francl, Michelle M ^a   Freed, Dana A ^a   Wray, Chandra C ^a   Hann, Christine ^a   Nerz Stormes, Maryellen ^a   Carroll, Patrick J ^b   Chirlian, Lisa E ^a  

^a BRYN MAWR COLLEGE   (United States)

^b UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FLUORINE; NAPHTHALENE DERIVATIVE;

ARTICLE; CALCULATION; CHEMICAL BINDING; CHEMICAL INTERACTION; CHEMICAL REACTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; THEORY;

EID: 0034600286     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993032z     Document Type: Article

References (35)

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9. The term "through-space" has long been used to designate the kind of coupling under consideration here. This term can be regarded as a misnomer, because the phenomenon involves scalar spin-spin coupling between pairs of fluorine nuclei in molecules that are freely tumbling in fluid solution, conditions under which direct through-space dipole-dipole interactions between the two fluorine nuclei are averaged to zero.
10. Here we are ignoring for simplicity the mixing of the fluorine PF lone-pair orbitals with orbitals of appropriate symmetry that are part of the a framework of the molecule bearing the fluorine substituents.
11. 3,4,12,14b
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15. FF = 17 Hz was reported for a pair of spatially proximate 6-fluorotryptophan residues in a particular polypeptide (an analogue of dihydrofolate reductase) whose primary structure is such that the shortest through-bond pathway between the two fluorines is 89 bonds long! See: Kimber, B. J.; Feeney, J.; Roberts, G. C. K.; Birdsall, B.; Griffiths, D. V.; Burgen, A. S. V.; Sykes, B. D. Nature 1978, 271, 184-185.
16. 9 in which the shortest through-bond pathway is seven bonds long.
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23. The partial double-bond character of the two-carbon bridge in dioxime 3f can be illustrated qualitatively by the resonance approach. (equation presented)
24. pa we attach no special significance to the numerical values of the slope and intercept given in eq 6. In particular, the interacting in-plane fluorine lone-pair orbitals on the two HF molecules in our model (see Figure 4) are pure 2p atomic orbitals, whereas in molecules of types 1 and 3 the corresponding interacting in-plane fluorine lone-pair orbitals are extensively mixed wilh various in-plane molecular orbitals associated with the carbon framework.
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27. 7 as the oxidant for the synthesis of acenaphthenequinones from the corresponding acenaphthenes.
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33. We are grateful to Dr. C. Daniel Yang for help in the preparation of this compound.
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35. We are grateful to John L. Dykins, the Director of the Mass Spectrometry Facility of the Department of Chemistry at the University of Pennsylvania, for the determination of this high-resolution mass spectrum.