Polyphosphorus Compounds Derived from P₄ Conversion with Sterically Demanding Cobalt Complexes

The conversion of P 4 with [Cp Bn Co(CO) 2 ] (Cp Bn =C 5 (CH 2 C 6 H 5 ) 5 ) under thermal conditions gives almost exclusively the P 10 complex [(Cp Bn Co) 4 (μ 4 ‐η 4 :η 4 :η 2 :η 2 :η 1 :η 1 ‐P 10 )]. However, its reaction with [Cp Bn Co] n , under mild conditions afforded a mixture of products including the P 8 species [(Cp Bn Co) 3 (μ 3 ‐η 4 :η 2 :η 2 :η 1 :η 1 ‐P 8 )] and a rare Co 3 cluster [(Cp Bn Co) 2 Co(μ 3 ‐η 5 :η 2 :η 1 :η 1 ‐C 40 H 33 )(μ‐H)(μ 3 ‐H)]. The products were studied in solution by multinuclear NMR spectroscopy and mass spectrometry and, for some compounds in the solid state, by single crystal X‐ray diffraction.