文摘
The electrophilic terminal aminophosphinidene complex [CpFe(CO)2P{N-i-Pr2}][X] (Cp?=?cyclopentadienyl, i-Pr?=?isopropyl, X?=?AlCl4 or NaBPh4), generated from [CpFe(CO)2{P(Cl)N-i-Pr2}] by chloride abstraction, reacts with alkynes and alkenes via (1?+?2) cycloaddition to form phosphirenes and phosphiranes respectively. Conjugated alkenes react with [CpFe(CO)2P{N-i-Pr2}]+ to form phosphirane intermediates, which then rearrange to 3-phospholenes. The phosphinidene complex reacts with benzylideneacetone to give an oxo-3-phospholene complex. Azobenzene reacts with [CpFe(CO)2P{N-i-Pr2}]+ to form a benzodiazophosphole via C-H activation. Addition of HCl or HBF4¡¤Et2O to the iron diphenylphosphirene complex and iron benzodiazophosphole complex results in P-N bond cleavage, yielding the respective chlorophosphorus heterocyclic complexes. The heterocycles can be removed from the metal complexes to make metal free phosphorus heterocycles by addition of trimethyl- or triethylphosphine.
