90498-59-2Relevant academic research and scientific papers
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)
Burford, Neil,Chivers, Tristram,Oakley, Richard T.,Oswald, Tom
, p. 712 - 715 (2007/10/02)
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 deg.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.
