SolidState NMR Study of HalogenBonded Adducts

Authors: David L Bryce Jasmine VigerGravel

Publish Date: 2014

Volume: , Issue: , Pages: 183-203

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Abstract

Nuclear magnetic resonance NMR spectroscopy offers unique insights into halogen bonds NMR parameters such as chemical shifts quadrupolar coupling constants J coupling constants and dipolar coupling constants are in principle sensitive to the formation and local structure of a halogen bond Carrying out NMR experiments on halogenbonded adducts in the solid state may provide several advantages over solution studies including 1 the absence of solvent which can interact with halogen bond donor sites and complicate spectral interpretation 2 the lack of a need for single crystals or even longrange crystalline order and 3 the potential to measure complete NMR interaction tensors rather than simply their isotropic values In this chapter we provide an overview of the NMR interactions and experiments which are relevant to the study of nuclei which are often found in halogen bonds RX···Y including 13C 35/37Cl 79/81Br 127I 77Se and 14/15N Experimental examples based on iodoperfluorobenzene halides bistrimethylammoniumalkane diiodide and selenocyanate complexes as well as haloanilinium halides are discussed Of particular interest is the sensitivity of the isotropic chemical shifts the chemical shift tensor spans and the halide nuclear electric quadrupolar coupling tensors to the halogen bond geometry in such compounds Technical limitations associated with the NMR spectroscopy of covalentlybonded halogens are underlined

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