Metallkomplexierte sulfinylphosphinite als intermediate bei der bildung von diphosphoxan-komplexen. Synthese, eigenschaften und struktur von μ-(tetraphenyldiphosphoxan)bisipentacarbonylmetall(0)lkomplexen, [(CO) 5MP(C 6H 5) 2] 2O (M = Cr, Mo, W)

Abstract

The diphenylphosphane complexes (CO) 5MP(C 6H 5) 2H (M = Cr, Mo, W) (Ia–Ic) react with sulfonyl chlorides, RSO 2Cl, (R = CH 3, p-CH 3C 6H 4) in diethyl ether via the non-isolable sulfinylphosphinito-P complexes (CO) 5M[P(C 6H 5) 2OS(O)R] (IIa–IIc) to give the homogeneous anhydrides, the diphosphoxane complexes [(CO) 5MP(C 6H 5) 2] 2O (IIIa–IIIc) and the sulfinylsulfones R(O)SS(O) 2R. The composition and structures of complexes III result from the IR, 31P NMR and mass spectra. The crystal structure of IIIa has been determined; IIIa crystallizes in the space group Cc. Two nearly octahedrally arranged (CO) 5CrP(C 6H 5) 2 moieties are joined by an unsymmetrical oxygen-bridge in the all- trans position, the bond angle P(1)OP(2) being 145°.