The thermal or photochemical reaction of [Cp′′Co(CO)2] (1) [Cp′′ = C5H3(SiMe3)2‐1,3] with white phosphorus (P4) gives [{Cp′′Co}2(P5–P5){CoCp′′}2] (2) and [{Cp′′Co}3P4(μ‐CO)] (3) as well as [{Cp′′Co}2(μ‐η2:η2‐P2)2] (4). Cobalt complexes 2, 3, and 4 have been characterized by an X‐ray crystal‐structure determination.
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