Burck Sebastian, Gudat Dietrich, Nieger Martin, Schalley Christoph A, Weilandt Torsten
Section Organic and Inorganic Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands.
Dalton Trans. 2008 Jul 14(26):3478-85. doi: 10.1039/b717219b. Epub 2008 Feb 28.
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.
对2-叠氮基-1,3,2-二氮磷杂环戊烯进行热解可得到新型且罕见的螺环环二磷氮烯。一种2-叠氮基-1,3,2-二氮磷杂环戊烯代表物的光谱数据和X射线结构揭示了一种离子键合情况，充分解释了其相当高的热稳定性。环二磷氮烯通过核磁共振、质谱和X射线衍射进行表征。电喷雾傅里叶变换离子回旋共振研究结果表明，这些化合物有可能通过λ5-二氮磷杂环戊烯环的[1,4]-环反转以及P2N2单元的对称裂解，在磷氮烯单元处发生还原消除反应。在其中一种环二磷氮烯的晶体中意外包含苯，这可以从分子识别的角度进行解释。化学反应研究包括磷氮烯环上双N-质子化的证明，以及通过选择性裂解磷氮烯P-N键进行的水解降解。
