83 / 2023-09-20 23:37:48

Carbazolyltetrylenes and P-C multiple bond species

Synthesis

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Tetrylenes have attracted great interest in molecular main group chemistry. In particular silylenes were intensively studied in recent years, and among them, the stabilisation of acyclic silylenes posed a challenge that was only solved in 2013.^[1,2] We have reported on the first dicoordinated halosilylenes which were supported by the bulky carbazole-based substituent ^dtbpCbz.^[3,4]

In this contribution, we will describe the metathesis chemistry of these tetrylenes, [(^dtbpCbz)EX] (E = Si, Ge, Sn, Pb; X = Cl, Br, I), with [Na(dioxane)_x]PCO which intermediarily leads to the formation of the corresponding phosphaketenyl-tetrylenes [(^dtbpCbz)EPCO]. These, in turn then undergo thermal or photolytical decarbonylation (Fig. 1).

Furthermore, in particular the halosilylenes react straightforwardly with phosphaalkynes, which allows the construction of small phosphorus-containing heterocycles as well as trapping of transient silylenes. These can be subjected to ring expansion reactions with isonitriles which will also be discussed.



Keywords：synthesis; hosphaketene; phosphaalkyne; tetrylenes

References

[1]        A. V. Protchenko, K. H. Birjkumar, D. Dange, A. D. Schwarz, D. Vidovic, C. Jones, N. Kaltsoyannis, P. Mountford, S. Aldridge, J. Am. Chem. Soc. 2012, 134, 6500–6503.

[2]         B. D. Rekken, T. M. Brown, J. C. Fettinger, H. M. Tuononen, P. P. Power, J. Am. Chem. Soc. 2012, 134, 6504–6507.

[3]         A. Hinz, Chem. Eur. J. 2019, 25, 3267–3271.

[4]         A. Hinz, Angew. Chem. Int. Ed. 2020, 59, 19065–19069.