Issue 5, 2017

(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles


Although BH3 simply coordinates the endocyclic P of (phospholidino)phosphaketene 1Dipp, the bulkier B(C6F5)3 gives rise to a zwitterionic diphosphirenium, which is a novel type of 2π-electron aromatic system as shown by the calculated NICS values. While the reaction of 1Dipp with Na[PCO(dioxane)x] is unselective, the same reaction with the sterically bulky (phospholidino)phosphaketene 1Ar** [Ar** = 2,6-bis[di(4-tert-butylphenyl)methyl]-4-methylphenyl selectively affords a sodium bridged dimer containing a hitherto unknown λ353-triphosphete core. The latter formally results from “P” addition to a 1,3-P/C-dipole. Similarly, adamantyl isonitrile adds to 1Dipp giving a 4-membered phosphacycle. In contrast to 1, the phosphaketene derived from the electrophilic diazaphospholidine-4,5-dione is unstable and reacts with a second molecule of Na[PCO(dioxane)x] to afford a 1,3,4-oxadiphospholonide derivative.

Graphical abstract: (Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles

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Article information

Article type
Edge Article
20 Jan 2017
07 Mar 2017
First published
08 Mar 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 3720-3725

(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles

M. M. Hansmann, D. A. Ruiz, L. L. Liu, R. Jazzar and G. Bertrand, Chem. Sci., 2017, 8, 3720 DOI: 10.1039/C7SC00300E

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