Electron rich backbones and bulky substituents of diphospha tetrylenes – theoretical and synthetic investigations

Elisabeth Schwarz, Ana Torvisco Gomez, Stefan Müller, Michaela Flock

Research output: Chapter in Book/Report/Conference proceedingConference paper


The amount of publications containing α,α‘- nitrogen stabilized heavier carbenes is quite large compared to the number of analogue α,α‘- phosphorus stabilized compounds. In fact, there is only one P-heterocyclic tetrylene known in literature.[1]
The p-donor capabilities of the phosphorus atom could be as large as those of the nitrogen. The difference in the electronegativities (Pauling: N = 3.04, P = 2.19) and the stronger pyramidalization of the phosphorus might counteract effective orbital overlap, which is necessary for the stabilization N- and P-heterocyclic compounds.
Most of the known diphospha tetrylenes are dimers. The dimerisation is favored with smaller, and non-interacting substituents. Compounds which provide higher stabilization by head-to- tail cycodaddition, are reported by du Mont[2], Cowley[3] and Buhro[4].
The stability of N-heterocyclic compounds is also increased with an electron rich backbone. Using calculations at the level of DFT the influence of various substituents (H, Me, tBu, tBu3Me, Ph, TMS, Hyp) and different suitable backbones, such as Ph, Mes, Mes*, 1,1’- binaphthalene, were investigated. The theoretical information, such as conformations and spectroscopic properties of the tetrylenes are used to identify suitable candidates for synthesis and product identification.

[1] Martin, D.; Baceiredo, A.; Gornitzka, H.; Schoeller W.W.; Bertrand, G.; Angew.Chem.Int.Ed., 2005, 44, 1700.
[2] du Mont, W. W.; Kroth, H. J. Angew. Chem. Int. Ed. Engl., 1977, 16(792).
[3] Cowley, A. H.; Giolando, D. M.; Jones, R. A.; Nunn, C. M.; Power, J. M. Polyhedron, 1988, 7(19-20)(1909).
[4]Subblash, C.; Michael, G.; Chiang, Y.; Rauscher, D. J.; Buhro, W. E. J. Am. Chem. Soc., 1993, 115, 160.
Original languageGerman
Title of host publicationElectron rich backbones and bulky substituents of diphospha tetrylenes – theoretical and synthetic investigations
Publication statusPublished - 11 Mar 2016

ASJC Scopus subject areas

  • Chemistry (miscellaneous)

Fields of Expertise

  • Advanced Materials Science


  • NAWI Graz

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