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1H and 199Hg NMR spectra of methylmercury(II)complexes. Effects of basicitv and ortho substitution in pyridines (L) in complexes [MeHgL]N03
journal contribution
posted on 2023-05-25, 22:08 authored by Canty, AJ, Barron, P, Healy, PCLinear complexes [MeHgL]NO3 (L = substituted pyridine) have been prepared and their 1H and 199Hg NMR spectra measured and compared with other complexes of this series reported previously. The coupling constant J(1H-199Hg) correlates directly with pKa and with the gas phase enthalpy of ionization [DGi(g) of LH+; with J(lH-199Hg) decreasing with increasing pKa or AGi(g). The chemical shift, delta, for 199Hg does not correlate with either pKa or AGi(g). Complexes without substituents in the 2 position of pyridine have delta l99Hg ca. 80-100 ppm downfield from MeHgN03, those with one methyl group in the 2 position ca. 125-150 ppm, and those with methyl groups in the 2 and 6 position (or benzyl or 3'-methylpyridyl groups in the 2 position) ca. 160-200 ppm downfield from MeHgN03. The coupling constant J(lH-l99Hg) is found to be more useful than delta 199Hg in determination of solution structures of MeHg(II) complexes of this type of ligand.
History
Publication title
Journal of Organometallic ChemistryVolume
179Article number
4Number
4Pagination
447-458ISSN
0022-328XPublication status
- Published
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