Takudrei

109
Phosphazene vs. diazaphospholene PN-bond cleavage in spirocyclic cyclodiphosphazenes

S. Burck, D. Gudat, M. Nieger, C. A. Schalley, T. Weilandt— 2008

Thermolysis of 2-azido-1,3,2-diazaphospholenes offers access to novel and rare spirocyclic cyclodiphosphazenes. The spectroscopic data and X-ray structure of one representative of the 2-azido-1,3,2-diazaphospholenes reveals an ionic bonding situation explaining sufficiently its rather high thermal stability. The cyclodiphosphazenes were characterised by NMR, mass spectrometry, and X-ray diffractometry. The results of ESI-FT-ICR studies demonstrate the potential of these compounds to undergo reductive elimination at a phosphazene unit via [1,4]-cycloreversion of a λ5-diazaphospholene ring, as well as symmetrical cleavage of the P2N2-unit. The unexpected inclusion of benzene in the crystal of one of the cyclodiphosphazenes was interpreted in terms of molecular recognition. Chemical reaction studies comprise the proof of double N-protonation at a phosphazene ring, and hydrolytic degradation via selective cleavage of a phosphazene P–N bond.

Title109
Phosphazene vs. diazaphospholene PN-bond cleavage in spirocyclic cyclodiphosphazenes
AuthorS. Burck, D. Gudat, M. Nieger, C. A. Schalley, T. Weilandt
Date20080228
IdentifierDOI 10.1039/B717219B
Source(s)
CitationDalton Trans. 2008, 3478-3485