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Group 6 metal (Cr, Mo, W) carbonyl complexes react with  cyclo -(P 5 Ph 5 ) to afford the phosphorus-rich complexes [Cr(CO) 5 { cyclo -(P 5 Ph 5 )-κ P  1 }] ( 1 ), [{Cr(CO) 5 } 2 {μ- cyclo -(P 5 Ph 5 )-κ P  1 , P  3 }] ( 2 ), [M(CO) 4 { cyclo -(P 5 Ph 5 )-κ P  1 , P  3 }] (with M=Cr ( 3 ), Mo ( 4 ), W ( exo - 5 ,  endo  -5 )) depending on the reaction conditions. Complexes  1–5  were characterised by  31 P{ 1 H} NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. The cyclopentaphosphane remains intact and acts as monodentate ( 1 ), bridging ( 2 ) or bidentate ( 3–5 ) ligand. Compounds  exo - 5  and  endo  -5  are configurational isomers and essentially differ in the orientations adopted by the phenyl rings attached to the uncoordinated phosphorus atoms. The  31 P{ 1 H} NMR spectra show five multiplets for an ABCDE spin system. Theoretical calculations showed that  exo - 5  and  endo - 5  are practically isoenergetic, which is in good agreement with the observed equilibrium in solution between  exo - 5  and  endo - 5 . The thermal properties of the complexes have also been evaluated.

Group 6 metal carbonyl complexes of cyclo -(P 5 Ph 5 )