(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles. Issue 5 (15th March 2017)

• Record Type: Journal Article
• Authors: Hansmann, Max M.; Ruiz, David A.; Liu, Liu (Leo); Jazzar, Rodolphe; Bertrand, Guy
• Is Part Of: Chemical science. Volume 8:Issue 5(2017)
• Page Start: 3720
• Page End: 3725
• Publication Date: 2017-03-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c7sc00300e
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Although BH3 simply coordinates the endocyclic P of (phospholidino)phosphaketene1 Dipp, the bulkier B(C6 F5 )3 gives rise to a zwitterionic diphosphirenium, which is a novel type of 2π-electron aromatic system as shown by the calculated NICS values. Abstract : Although BH3 simply coordinates the endocyclic P of (phospholidino)phosphaketene1 Dipp, the bulkier B(C6 F5 )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 of1 Dipp with Na[PCO(dioxane) x ] is unselective, the same reaction with the sterically bulky (phospholidino)phosphaketene1 Ar** [Ar** = 2, 6-bis[di(4- tert -butylphenyl)methyl]-4-methylphenyl selectively affords a sodium bridged dimer containing a hitherto unknown λ 3, λ 5, λ 3 -triphosphete core. The latter formally results from "P − " addition to a 1, 3-P/C-dipole. Similarly, adamantyl isonitrile adds to1 Dipp giving a 4-membered phosphacycle. In contrast to1, 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.