Reduction of the Fe complex [( PP )FeCl ] (2) generated an electron-rich and unsaturated Fe species, which was reacted with white phosphorus. The resulting new complex, [( PP )Fe(η -P )] (3), is the first iron cyclo-P complex and the only known stable end-deck cyclo-P complex outside Group V. Complex 3 features an Fe center, as shown by Mössbauer spectroscopy, associated to a P fragment. The distinct reactivity of complex 3 was rationalized by analysis of the molecular orbitals. Reaction of complex 3 with H afforded the unstable complex [( PP )Fe(η -P )(H)] (4), whereas with CuCl and BCF, the complexes [( PP )Fe(η :η -P )(μ-CuCl)] (5) and [( PP )Fe(η :η -P )B(C F ) ] (6) were formed.
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