C-C bond insertion of a complexed phosphinidene into 1,6-methano[10]annulene

Chemistry : a European Journal
Rosa E BuloKoop Lammertsma

Abstract

Reaction of electrophilic phosphinidene complex [MePW(CO)5] with 1,6-methano-[10]annulene results in the sole formation of the isomeric C-C insertion products 6 c (main) and 6 d (minor). The single-crystal X-ray structure of the complexed 1,7-methano-3-phospha[11]annulene (6 c) shows a syn-W(CO)5 group at the exo bent phosphorus. The structure displays C-C bond alternation without bonding between the bridgehead carbon atoms. Density functional theory calculations indicate 6 c to result from a concerted disrotatory ring opening of an undetected tricyclic exo-syn phosphirane intermediate. The endo-anti phosphirane cannot undergo ring expansion, due to the high barrier that is associated with an intramolecular antara-antara retro Diels-Alder reaction. The stabilizing effect of transition-metal coordination is discussed.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes
Jun 19, 1998·Angewandte Chemie·Maurice J van EisAnthony L Spek

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Citations

May 24, 2017·The Journal of Physical Chemistry. a·Laura MoroniCristina Gellini
Mar 19, 2019·Chemistry : a European Journal·Martin PieschManfred Scheer
Apr 14, 2010·Chemical Reviews·L Kollár, G Keglevich
Dec 8, 2020·Journal of the American Chemical Society·Junjian WangFrançois Mathey
Dec 1, 2005·Journal of the American Chemical Society·Mark L G BorstKoop Lammertsma

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