Aspects of Phosphaallene Chemistry: Heat-Induced Formation of 1,2-Dihydrophosphetes by Intramolecular Nucleophilic Aromatic Substitution and Photochemical Generation of Tricyclic Phosphiranes.

3H-Phosphaallenes are accessible on a new and facile route and show a fascinating chemical behavior. The thermally induced rearrangement of Mes*P═C═C(H)R' (R' = tBu, Ad) afforded by C-H activation, isobutene elimination, and C-C and P-H bond formation bicyclic 1-benzo-dihydrophosphetes (2) with PC3 heterocycles. DFT calculations suggest a mechanism with intramolecular nucleophilic aromatic substitution and replacement of an alkyl group by the nucleophilic α-C atom of the phosphaallene. These bicycles formed W(CO)5 complexes (3) or afforded 1,2-dihydrophosphetes with P-bound alkenyl groups by catalyst-free hydrophosphination of alkynes (4 and 5). The resulting bulky phosphines formed complexes with IrCp*Cl2, RuCl2, AuCl, or CuO3SCF3. The Ru atom is coordinated by the P atom and a phenyl group. Irradiation of TripP═C═C(H)tBu led by the insertion of the central C atom of the P═C═C group into the α-C-H bond of an iPr substituent and by C-C and P-C bond formation to a new isomer of phosphaallenes, 10, which features a strained PC2 heterocycle. It formed adducts with M(CO)5 (M = Cr, Mo, W) and AuCl and reacted with SO2Cl2 by cleavage of one of the phosphirane P-C bonds to yield PC4 or PC5 heterocycles. Hydrolysis yielded a PC5 compound with a P(O)Cl group.