An improved <sup>33</sup>S nuclear magnetic shielding scale from the gas‐phase study of COS

Jackowski, Karol; Makulski, Włodzimierz; Koźmiński, Wiktor

doi:10.1002/mrc.1062

Cited by 26 publications

(27 citation statements)

References 17 publications

(17 reference statements)

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“…Ideally, one could do this by using the experimental 33 S absolute shielding scale. [46][47][48] The existing scale, 47,48 however, is for diluted gases and would require a correction for the effect of intermolecular interactions in CS 2 . The effect is unknown, but may be as large as tens of ppm.…”

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confidence: 99%

High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

et al. 2009

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=0b178185-620e-4262-8966-6e518a9bdcdf http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=0b178185-620e-4262-8966-6e518a9bdcdf High Field S Solid State NMR and First-Principles Calculations in Potassium SulfatesIgor Moudrakovski,* Stephen Lang, Serguei Patchkovskii, and John Ripmeester Steacie Institute for Molecular Sciences, National Research Council, 100 Sussex DriVe, Ottawa, K1A 0R6, Ontario, Canada ReceiVed: August 25, 2009; ReVised Manuscript ReceiVed: October 16, 2009 A set of potassium sulfates presenting a variety of sulfur environments (K 2 SO 4 , KHSO 4 ,K 2 S 2 O 7 , and K 2 S 2 O 8 ) has been studied by 33 S solid state NMR at 21 T. Low natural abundance (0.75%) and small gyromagnetic ratio of 33 S presented a serious challenge even at such a high magnetic field. Nevertheless, using the QCPMG technique we were able to obtain good signals from the sites with C Q values approaching 16 MHz. Assignment of the sites and the relative orientations of the EFG tensors were assisted by quantum mechanical calculations using the Gaussian 98 and CASTEP packages. The Gaussian 98 calculations were performed using the density functional method and gauge independent atomic orbitals on molecular clusters of about 100-120 atoms. The CASTEP calculations utilized periodic boundary conditions and a gauge-including projector augmentedwave pseudopotential approach. Although only semiquantitative agreement is observed between the experimental and calculated parameters, the calculations are a very useful aid in the interpretation of experimental data.

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High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

et al. 2009

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“…To determine the absolute shieldings for the two R 3 PS compounds, we measured the shifts relative to CS 2 which has an absolute shielding of 536.1. 35 The spectra were of very poor quality, unlike those of the two reference compounds, and gave very broad peaks (full width at halfheight of 100 ppm or more) on severely rolling baselines due to acoustic ringing, even when using an anti-ring pulse program. The experimental shifts that we report here must be considered highly tentative at this time.…”

Section: Comparison Of Theory and Experimentsmentioning

confidence: 99%

Bonding and33S NMR chemical shielding in the thiophosphoryl group

2004

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B3LYP and MP2 calculations at the 6-311 + G(nd,p) level (with n = 2 for second-row elements and n = 1 otherwise) were carried out using the atoms-in-molecules (AIM) approach to characterize the thiophosphoryl bond. A series of R(3)PS molecules were studied and compared with the corresponding R(3)PO systems. As with the phosphoryl bond, one cannot distinguish the thiophosphoryl bond from a standard P=S double bond by comparing bond distances. On the basis of the P=S bond in HP=S having a reference bond order of 2.0, the thiophosphoryl bond has a bond order of about 1.6. Examination of localized orbitals show that this bond is less polar than the corresponding PO bond. As with the phosphoryl bond, what sets the thiophosphoryl bond apart is the high degree of back-bonding that contributes to the delocalization index (and covalent bond order) and is the basis for its stronger than single bond character and short bond distance. (33)S NMR shielding calculations were also carried out and, in a few instances, compared directly with newly determined experimental shieldings.

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“…The S-methyl-tetrahydrothiophenium Cation Annunziata and Barbarella [35] report a chemical shift for S-methyl tetrahydrothiophenium iodide 8I (as a saturated solution in chloroform, liquid dielectric constant of about five) of 750 ± 50 ppm downfield of CS 2 with a line width of 390 ± 50 ppm. Using the new absolute shielding scale [28] for CS 2 one arrives at an absolute shielding of −214 ppm for this compound. This shielding is currently thought to be the most downfield observed shielding of any sulfur compound.…”

Section: The R 3 Ps Species; Hps 2 and Its Dimersmentioning

confidence: 99%

“…We converted chemical shifts to absolute shieldings using the new sulfur shielding scale of Jackowski, Makulski, and Koźmiński [28] in which liquid OCS at 295 K has an absolute shielding of 798.5; these authors also present absolute shieldings for H 2 S, CS 2 , SF 6 , and SO 2 . Gas phase values for shielding, such as 817 for OCS, were employed where available.…”

Section: Calculationsmentioning

confidence: 99%

³³S NMR shieldings and chemical bonding in compounds of sulfur

Chesnut

Quin

2004

Heteroatom Chemistry

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An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

Cited by 26 publications

References 17 publications

High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

Bonding and33S NMR chemical shielding in the thiophosphoryl group

³³S NMR shieldings and chemical bonding in compounds of sulfur

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An improved 33S nuclear magnetic shielding scale from the gas‐phase study of COS

Cited by 26 publications

References 17 publications

High Field 33S Solid State NMR and First-Principles Calculations in Potassium Sulfates

High Field 33S Solid State NMR and First-Principles Calculations in Potassium Sulfates

Bonding and33S NMR chemical shielding in the thiophosphoryl group

33S NMR shieldings and chemical bonding in compounds of sulfur

Contact Info

Product

Resources

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An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

High Field ³³S Solid State NMR and First-Principles Calculations in Potassium Sulfates

³³S NMR shieldings and chemical bonding in compounds of sulfur