Satellite transitions in MAS NMR spectra of quadrupolar nuclei

Skibsted, Jørgen; Nielsen, Niels Chr.; Bildsøe, Henrik; Jakobsen, Hans J.

doi:10.1016/0022-2364(91)90327-p

Cited by 190 publications

(237 citation statements)

References 32 publications

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“…In the present case, the magnitude of the quadrupolar coupling constant was obtained by simulations of a single site; the breadth of the resulting line shape was matched to the experimental spectrum. Additionally, an upper limit on the asymmetry parameters of 0.25 was ascertained by comparing SATRAS simulations 1,39 to a spectrum acquired experimentally. Attempts to fit the spectra based on the assumption of a single crystallographic site were fruitless.…”

Section: Resultsmentioning

confidence: 99%

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Bryce

Wasylishen

1999

J. Phys. Chem. A

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Despite the favorable NMR properties of 9 Be (I ) 3 / 2 ), NMR spectroscopy of this nucleus in the solid state remains comparatively unexplored, perhaps owing to the extreme toxicity of beryllium and its compounds. We present here an integrated experimental and theoretical study of the Be chemical shielding (CS) and electric field gradient (EFG) tensors in bis(2,4-pentanedionato-O,O′)beryllium [Be(acac) 2 ]. Interpretation of the 9 Be NMR data was facilitated by crystal X-ray diffraction results, which indicate two crystallographically unique sites (Onuma, S.; Shibata, S. Acta Crystallogr. 1985, C41, 1181). Beryllium-9 NMR spectra acquired at 4.7 and 9.4 T for magic-angle spinning (MAS) and stationary samples have been fitted in order to extract the nuclear quadrupole coupling constant (C Q ), asymmetry parameter (η), and isotropic chemical shift (δ iso ). The best-fit nuclear quadrupole parameters for the two sites were determined to be C Q (1) ) -294 ( 4 kHz, η(1) ) 0.11 ( 0.04; C Q (2) ) -300 ( 4 kHz, η(2) ) 0.15 ( 0.02. Our analyses of the stationary samples also reveal a definite anisotropy in the beryllium CS tensor and allow us to place upper and lower limits on the spans of 7 and 3 ppm. This is the first evidence for anisotropic shielding in beryllium. Ab initio calculations of the beryllium CS tensors in Be(acac) 2 at the RHF level indicate spans ranging from 7 to 9 ppm; this represents a substantial fraction of the total known chemical shift range for Be (<50 ppm). The calculated C Q s are also in good agreement with the experimental results. To put the Be(acac) 2 results in context, calculations of the beryllium CS tensors for a series of compounds encompassing the known range of 9 Be chemical shifts are also presented. The calculations are in outstanding accord with experimental data from the literature. On the basis of calculations for linear molecules, it is shown that the assumption that the 9 Be chemical shift is governed essentially by the diamagnetic term is erroneous. For some of these molecules, the calculated Be CS tensor spans are greater than the total known chemical shift range.

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Section: Resultsmentioning

confidence: 99%

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Bryce

Wasylishen

1999

J. Phys. Chem. A

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“…24). This simulation was carried out with a modified version of the STARS software developed previously to analyze satellite transition MAS spectra from half-integer quadrupolar nuclei [107]. In addition to the quadrupolar interaction and CSA (known from 15 N experiments), second-order cross terms [108] between these interactions were included, as well as the effects of various experimental factors such as the limited probe bandwidth and small deviations from the magic angle.…”

Section: Broadband Excitationmentioning

confidence: 99%

Direct detection of nitrogen-14 in solid-state NMR spectroscopy

O’Dell¹

2011

Progress in Nuclear Magnetic Resonance Spectroscopy

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“…For example, in a magnetic field of 11.75 T, MAS NMR at 15 kHz on a sample containing chlorine sites with values of C Q 35 Cl of up to approximately 3 MHz results in a CT spectrum with resolved spinning sidebands. Satellitetransition spectroscopy (SATRAS) 128,150,151 is also useful for the quadrupolar halogens when nuclear quadrupolar coupling constants are relatively small.…”

Section: Powdered Samplesmentioning

confidence: 99%

Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127

Bryce

Sward

2006

Magn. Reson. Chem.

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Satellite transitions in MAS NMR spectra of quadrupolar nuclei

Cited by 190 publications

References 32 publications

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Direct detection of nitrogen-14 in solid-state NMR spectroscopy

Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127

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Satellite transitions in MAS NMR spectra of quadrupolar nuclei

Cited by 190 publications

References 32 publications

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of 9Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of 9Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Direct detection of nitrogen-14 in solid-state NMR spectroscopy

Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127

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Product

Resources

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Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding

Beryllium-9 NMR Study of Solid Bis(2,4-pentanedionato-O,O‘)beryllium and Theoretical Studies of ⁹Be Electric Field Gradient and Chemical Shielding Tensors. First Evidence for Anisotropic Beryllium Shielding