The gas-phase i.r. and liquid-phase Raman spectra of the phosphines CF,-PX, (X = H, F, CI. Br. or I) have been recorded. The observed bands have been assigned on the basis of C, symmetry. However, there is substantial mixing of the internal co-ordinates of vibration, and so simple group-frequency correlations cannot be made for all of the bands. The coupling of vibrations is less severe in the case of CF,PH,.

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upon Tyne NE1 7RUThe monomeric phosphido-complex, (X-C,H~)F~(CO),P(CF~)~. which is prepared from (CF,),P.P(CF,), and [(x-C,H,)Fe(CO),],, can be converted to (x-C,H,)Fe(CO),P(E)(CF,), by the action of nitric oxide ( E = 0),sulphur (E = S), or selenium (E = Se). Other routes to the sulphur compound have been devised. The action of U.V. radiation upon (x-C5H5) Fe(CO),P(CF,), gives the expected dimer in a vans-configuration, whereas (x-C,H,)Fe(CO),P(O)(CF,),gives a new type of trimer, (C5H5),Fe,(CO),[OP(CF,),14, as the major product. Upon photolysis, (x-C5H5)Fe(CO),P(E)(CF,), give the isomeric complexes (x-C5H5)Fe(CO),EP(CF,), (E = S or Se). The preparation of (r-C,H,)Fe(CO),SP(S) (CF,), from the sulphur complex is also reported. Spectroscopic data for all the compounds prepared are discussed.RECENT investigations have demonstrated that secondary phosphines co-ordinated to transition metals can rearrange by transfer of hydrogen from phosphorus to the metal l~~ or to other ligands.3-, In co-ordinated phosphines, the lone pair on phosphorus is normally regarded as used in o-bond formation with the metal. diphosphine (CF,),P*P(CF,),, upon [(x-C,H,)Fe(CO)J,, or, less efficiently, from the iron dimer and bis(trifluor0-methy1)phosphine. The former route is exactly analogous to that reported by Cullen and Hayter for the preparation of (n-C,H5)Fe(CO),As(CF,)2. Spectroscopic data for compound (I) are given in Table 1. Attention TABLE 1Spectroscopic data for some derivatives of (x-C5H,) Fe(C0) 2P(CF,),

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