P4 inserts into the Ru–Cl bond of [RuCl(Cp*)(PCy3)], yielding the unprecedented P4Cl2 moiety which can be selectively alkylated to [P4nBu2].

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The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low‐valent transition‐metal species [Cp′′′Co] (Cp′′′=η5‐C5H2‐1,2,4‐tBu3) and [L0M] (L0=CH[CHN(2,6‐Me2C6H3)]2; M=Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P–P edges and the formation of a square‐planar cyclo‐P4 ligand. The reaction products [{CpRu(PPh3)2}{CoCp′′′}(μ,η1:4‐P4)][CF3SO3] (5), [{CpBIGMn(CO)2}2{CoCp′′′}(μ,η1:1:4‐P4)] (6) and [{CpBIGMn(CO)2}2{ML0}(μ,η1:1:4‐P4)] (CpBIG=C5(C6H4nBu)5; L0=CH[CHN(2,6‐Me2C6H3)]2; M=Fe (7 a), Co (7 b)), respectively, were fully characterized by single‐crystal X‐ray diffraction and spectroscopic methods. The electronic structure of the cyclo‐P4 ligand in the complexes 5–7 is best described as a π‐delocalized P42− system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5, in which a quasi‐butterfly‐shaped P4 moiety bridges the two metals and behaves as an η3‐coordinated ligand towards the cobalt center.

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