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Updated: Jun 21, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
GIPAW (gauge including projected augmented wave) and local dynamics in 13C and 29Si solid state NMR: the study case
Christel Gervais1, Laure Bonhomme-Coury, Francesco Mauri
1Laboratoire de Chimie de la Matière Condensée de Paris, UMR CNRS 7574, Université Pierre et Marie Curie, Collège de France, Paris, France. christel.gervais_stary@upmc.fr
Abstract:
Octameric silsesquioxanes (RSiO(1.5))(8) are versatile and interesting nano building blocks, suitable for the synthesis of nanocomposites with controlled porosity. In this paper, we revisit the (29)Si and (13)C solid state NMR spectroscopy for this class of materials, by using GIPAW (gauge including projected augmented wave) first principles calculations [Pickard & Mauri, Phys. Rev. B, 2001, 63, 245101]. Full tensorial data, including the chemical shift anisotropies (CSA) and the absolute orientation of the corresponding principal axes systems (PAS), were calculated. Subsequent averaging of the calculated tensors (due to fast reorientation of the R groups around the Si-C bonds) allowed for the interpretation of the strong reduction of CSA and dipolar couplings for these derivatives. Good agreement was observed between the averaged calculated data and the experimental parameters. Interesting questions related to the interplay between X-ray crystallography and solid state NMR are raised and will be emphasized.
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