Claire Tessier - Structure and Conformation of the Medium-Sized Chlorophosphazene Rings

Document created by Claire Tessier on Apr 25, 2015
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  Bowers, David J., Wright, Brian D., Scionti, Vincenzo, Schultz,   Anthony, Panzner, Matthew J., Twum, Eric B., Li, Lin-Lin,   Katzenmeyer, Bryan C., Thome, Benjamin S., Rinaldi, Peter L.,   Wesdemiotis, Chrys, Youngs, Wiley J., Tessier, Claire A.   Inorganic Chemistry 2014 53  (17) 8874-8886

  Abstract: Medium-sized cyclic oligomeric   phosphazenes [PCl2N]m (where m = 5?9) that were prepared from the   reaction of PCl5 and NH4Cl in refluxing chlorobenzene have been   isolated by a combination of sublimation/extraction and column   chromatography from the predominant products [PCl2N]3 and   [PCl2N]4. The medium-sized rings [PCl2N]m have been characterized   by electrospray ionization?mass spectroscopy (ESI-MS), their 31P   chemical shifts have been reassigned, and their T1 relaxation   times have been obtained. Crystallographic data has been   recollected for [PCl2N]5, and the crystal structures of [PCl2N]6,   and [PCl2N]8 are reported. Halogen-bonding interactions were   observed in all the crystal structures of cyclic [PCl2N]m (m =   3?5, 6, 8). The crystal structures of [P(OPh)2N]7 and   [P(OPh)2N]8, which are derivatives of the respective [PCl2N]m,   are also reported. Comparisons of the intermolecular forces and   torsion angles of [PCl2N]8 and [P(OPh)2N]8 with those of three   other octameric rings are described. The comparisons show that   chlorophosphazenes should not be considered prototypical, in   terms of solid-state structure, because of the strong influence   of halogen bonding.

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