Komplexe mit Metall‐Phosphor‐Dreifachbindungen als mögliche Intermediate der Umsetzungen von Chlorophosphiniden‐Komplexen mit Metallaten verschiedener Übergangsmetalle

Complexes with Metal‐Phosphorus Triple Bonds as Possible Intermediates in the Reactions between Chlorophosphinidenes and Metalates of Various Transition Metals The reaction of [{M′(CO) 5 } 2 PCl] (M′ = Cr, W) with various metalates ([Cp′Mo(CO) 3 ] − , [Cp * Ni(CO)] − , [Cr 2 (CO) 10 ] 2− ) yields the M 2 P 2 tetrahedral complexes [(ML n ) 2 (μ,η 2 ‐ P 2 ){M′(CO) 5 } 2 ] (ML n = Cp*Ni, M′= Cr ( 1 ), W ( 2 ); ML n = Cp′Mo(CO) 2 , M′ = Cr ( 4 ); Cp* = η 5 ‐C 5 Me 5 , Cp* = η 5 C 5 H 3 t Bu 2 ) and the cyclo ‐P 4 compound [{Cr(CO) 4 }(η 4 ‐P 4 ){Cr(CO) 5 } 4 ] 6 . As side products the distorted prismane [(Cp*Ni) 2 {μ 4 ,η 4 ‐(P 2 ‐O‐P 2 )}{W(CO) 5 } 2 ] 3 and the diphosphino‐methanone complex [{Cp′Mo(CO) 2 } 2 {μ 4 η 2 ‐PC(O)P}‐{Cr(CO) 5 } 2 ] 5 are formed. The complexes are characterised by NMR, IR, MS, and X‐ray structure analysis ( 1‐5 ). Studying the reaction pathway provided evidence of phosphido intermediates of the type [L n MP→M′L n ].