Overcrowded aminophospanitrenes: A case study

Tirrée, Jürgen and Ruban, Alexander V. and Nieger, Martin and Li, Claudia and Nyulászi, László and Niecke, Edgar (2017) Overcrowded aminophospanitrenes: A case study. ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 72 (11). pp. 865-871. ISSN 0932-0776

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Abstract

In a search for stable phosphinonitrenes generated by thermally induced decomposition of the azidophosphines 8a, b, different cyclodiphosp(V)azene products were generated. While in the case of 8a the expected phosphinonitrene dimer 10 could be obtained, from 8b, which has the sterically more demanding TMP substituents, product 11, was obtained and characterized. DFT calculations have revealed that the primarily formed phosphinonitrene 9b is unstable against loss of TMP', and the resulting radical dimerizes to the biradicaloid 1,3-diaza-2,4-diphosphetane-2,4-diyl 13. Compound 13 then dimerizes after ring opening, yielding in the ring system, which provides the final product upon reaction with the starting azidophosphine.

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