Alkaline-earth metal carboxylates characterized by 43Ca and 87Sr solid-state NMR: impact of metal-amine bonding

Inorganic Chemistry
Kevin M N BurgessDavid L Bryce

Abstract

A series of calcium and strontium complexes featuring aryl carboxylate ligands has been prepared and characterized by alkaline-earth ((43)Ca and (87)Sr) solid-state NMR experiments in a magnetic field of 21.1 T. In the 11 compounds studied as part of this work, a range of coordination motifs are observed including nitrogen atom binding to Ca(2+) and Sr(2+), a binding mode which has not been investigated previously by (43)Ca or (87)Sr solid-state NMR. (43)Ca isotopic enrichment has enabled the full characterization of the (43)Ca electric field gradient (EFG) and chemical shift tensors of the two calcium sites in calcium p-aminosalicylate (Ca(pams)), where both NMR interactions are affected by the presence of a nitrogen atom in the first coordination sphere of one of the metal sites. The (43)Ca isotropic chemical shift is sensitive to the Ca-N distance as exemplified by the NMR parameters of a second form of Ca(pams) and density functional theory (DFT) calculations. Studies of the strontium analogue, Sr(pams), confirm a similar sensitivity of the (87)Sr EFG tensor to the presence or absence of nitrogen in the first coordination sphere. To our knowledge, this is the first systematic (87)Sr NMR study of strontium complexes featurin...Continue Reading

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Nov 14, 2015·The Journal of Physical Chemistry. a·Alexandra FaucherRoderick E Wasylishen
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May 31, 2014·Physical Chemistry Chemical Physics : PCCP·Cory M WiddifieldDavid L Bryce
Oct 9, 2014·Journal of the American Chemical Society·Sharon E Ashbrook, Scott Sneddon

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