The short-time cothermolysis of [{Cp‘‘‘(OC)2Fe}2](Fe−Fe) (1) and white phosphorus, P4, in toluene gives the butterfly complex [{Cp‘‘‘(OC)2Fe}2(μ-η1:η1-P4)] (2), Cp‘‘‘ = C5H2But 3-1,2,4, as the only product in 75% isolated yield. The open-edged exo/exo-P4 derivative 2 where one of the six P−P bonds of P4 has been selectively cleaved gives, on thermolysis, the sandwich complexes [Cp‘‘‘Fe(η5-P5)] (3) and [{Cp‘‘‘Fe}2 (μ-η4:η4-P4)] (4) with a cisoid P4 chain.

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