1H and 199Hg NMR spectra of methylmercury(II) complexes. Effects of basicity and ortho substitution in pyridines(L) in complexes [MeHgL]NO3 |
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Authors: | Allan J. Canty Peter Barron Peter C. Healy |
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Affiliation: | Department of Chemistry, University of Tasmania, Hobart, Tasmania, 7001 Australia;School of Science, Griffith University, Nathan, Queensland, 4111 Australia |
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Abstract: | Linear 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 [ΔGi(g)] of LH+; with J(1H?199Hg) decreasing with increasing pKa or ΔGi(g). The chemical shift, δ, for 199Hg does not correlate with either pKa or ΔGi(g). Complexes without substituents in the 2 position of pyridine have δ199Hg ca. 80–100 ppm downfield from MeHgNO3, 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 MeHgNO3. The coupling constant J(1H?199Hg) is found to be more useful than δ199Hg in determination of solution structures of MeHg(II) complexes of this type of ligand. |
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