title: Phosphazene vs.diazaphospholene PN-bond cleavage in spirocyclic cyclodiphosphazenes.
abstract: 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 lambda5-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.
authors.affiliation: Section Organic and Inorganic Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Burck
authors.forename: Dietrich
authors.initials: D
authors.lastname: Gudat
authors.forename: Martin
authors.initials: M
authors.lastname: Nieger
authors.forename: Christoph A
authors.initials: CA
authors.lastname: Schalley
authors.forename: Torsten
authors.initials: T
authors.lastname: Weilandt