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DOI: 10.1039/A903119G (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 2163-2170

Investigation of solute–solvent interactions in a dithiophosphoroorganic carbohydrate derivative by means of X-ray analysis and solid state NMR

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Marek J. Potrzebowski, Katarzyna Ganicz, Włodzimierz Ciesielski, Aleksandra Skowrońska, Michał W. Wieczorek, Jarosław Błaszczyk and Wiesław Majzner

Abstract

Bis[6-O,6′-O-(1,2∶3,4-diisopropylidene-α-D-galactopyranosyl)thiophosphoryl] disulfide 1 (C48H76O24P2S4) crystallized from polar and/or nonpolar solvents forms different inclusion complexes and solvates. The X-ray data for complexes of 1 with propan-2-ol (1a) and acetone (1b) are reported. From DSC measurements it is apparent that with loss of the solvent, crystals undergo complex rearrangements below the melting point forming the 1c modification. Each form is characterized by 31P CP/MAS experiment. The analysis of the 31P δii principal elements of the chemical shift tensor suggests that distinction of δ33 for different modifications is related to O–H[hair space][hair space]· · ·[hair space][hair space]S[double bond, length half m-dash]P and C–H[hair space][hair space]· · ·[hair space][hair space]S[double bond, length half m-dash]P intermolecular contacts. 2H NMR spectroscopy is employed to investigate the mechanism of phase reorientation and molecular dynamics of methyls of the isopropylidene blocking groups. At ambient temperature, the C3v jump of the methyl group and additional small-amplitude motion of the five membered ring is deduced from line-shape analysis of a 2H QUADECHO experiment. During the change of sample composition at 370 K, fast molecular motion of the methyl groups is observed while the S[double bond, length half m-dash]P–S–S–P[double bond, length half m-dash]S backbone remains rigid. From variable temperature 2H T1 inversion–recovery measurements it is concluded that the Ea of the C3v jump strongly depends on molecular packing.

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