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Although BH 3 simply coordinates the endocyclic P of (phospholidino)phosphaketene 1Dipp , the bulkier B(C 6 F 5 ) 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 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 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.