Activation of a 1‐Chlorophosphirane Complex by Aluminum Trichloride: Generation and Trapping of [Fc‐P‐W(CO)₅] (Fc = Ferrocenyl)

Abstract

Aluminum trichloride catalyzes the ring opening of a 1‐chlorophosphirane W(CO)5 complex and its reaction with thiophene and ferrocene to give the corresponding 1‐(2‐thienyl)‐ and 1‐ferrocenylphosphirane derivatives. The W(CO)5 complex of the 1‐ferrocenylphosphirane is an efficient precursor of the phosphinidene complex [FcP‐W(CO)5], which is trapped by tolan, trans‐stilbene, and water.

Sequential electrophilic P–C bond formation in metal-coordinated chlorophosphines

“…A similar mechanism has been described in a related chlorophosphirane system. 14 The limited functional group tolerance of the AlCl 3 methodology led us to consider silver triflate as an alternative. Compound 1 reacts with silver triflate to form diphenyl phosphine triflate complex 3.…”

Isomerization of Secondary Phosphirane into Terminal Phosphinidene Complexes: An Analogy between Monovalent Phosphorus and Transition Metals

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Secondary phosphirane complexes isomerizeabove 100 8 8Ct og ive the corresponding terminal phosphinidene complexes,w hichc an be trapped by alkenes and alkynes. [2,3] This observation led us to investigate the reduction of the chloro derivatives 1 [2] to obtain ap otential precursor of [HP-W(CO) 5 ]. [1] They have been generated with av ariety of substituents,b ut the parent species are still not accessible.W eh ave recently shown that the phosphirane complexes derived from cyclohexene are good precursors for [RP-W(CO) 5 ]( R = Cl, Fc).

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“…[1] They have been generated with av ariety of substituents,b ut the parent species are still not accessible.W eh ave recently shown that the phosphirane complexes derived from cyclohexene are good precursors for [RP-W(CO) 5 ]( R = Cl, Fc). [2,3] This observation led us to investigate the reduction of the chloro derivatives 1 [2] to obtain ap otential precursor of [HP-W(CO) 5 ]. After several attempts (NaH, LiAlH 4 ), we found that Bu 3 SnH was the reagent of choice,t hus giving 2a,b in 59 %y ield [Eq.…”

Developing a new phosphorus-carbon bond synthesis

“…Electrophilic substitutions involving phosphiranyl and phosphirenyl cations have also been reported recently (Scheme 1.108). [333][334] Bulky groups such as ferrocene can be introduced onto P atom of the phosphirane and phosphirene. There is a recent report on electrophilic substitution reactions between phosphirenyl triflate and heterocycles.…”