Synthetic and kinetic studies of the reversible addition of a bridging NSN fragment to the electron-rich heterocycles (R2PN)(SN)2 (R = Me, Ph, F)
- 1 April 1984
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 62 (4) , 712-715
- https://doi.org/10.1139/v84-119
Abstract
The oxidative addition of Cl2 (using SO2Cl2) to the six-membered ring (R2PN)(SN)2 (R = Me, Ph) produces the mixed phosphazene–thiazyl heterocycles, (R2PN)(NSCl)2, which react with Me3SiNSNSiMe3 to give the bicyclic compounds R2PS3N5. The latter undergo thermal decomposition, at ca. 100 °C in toluene, via reductive elimination of an NSN unit to regenerate (R2PN)(SN)2 in high yield. Kinetic measurements of this process, using 31P nmr spectroscopy, yield an activation energy of 102.4 ± 6.0 kJ mol−1 for the release of the NSN fragment from Me2PS3N5. The thermolysis route has been used to prepare the thermally unstable (F2PN)(SN)2, characterized as a 1:1 adduct with norbornadiene.Keywords
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