Difluoro complexes of platinum(II) and -(IV) with monodentate phosphine ligands: an exceptional stability of d6 octahedral organometallic fluorides.

Complexes (R3P)2PtF2 were prepared by reaction of the corresponding diiodo precursors with AgF in dichloromethane. The intermediate formation of trans- and cis-(R3P)2Pt(I)F was also observed. All fluoro complexes demonstrate a strong preference for the cis-configuration (R = Ph or Et) unless a bulky phosphine ligand is used (R = i-Pr), in which case the trans complex was observed. The Pt(IV) difluoro compounds (R3P)2Ar2PtF2 were obtained by reacting the Pt(II) diaryl precursors with XeF2. The fluoro ligands are located in the trans-position relative to the aryl groups in the overall octahedral environment. The representative Pt(II) and Pt(IV) difluoro complexes were characterized by X-ray crystallography. All fluoro compounds react rapidly with chlorotrimethylsilane to give the corresponding chloro complexes. The Pt(IV) difluorides are remarkably stable in the C-C reductive elimination reaction, relative to their dichloro analogs which reductively eliminate diaryl within several hours at 45 degrees C in N-methylpyrrolidone. It was found that phosphine dissociation from the octahedral Pt(IV) complex is essential for the reductive elimination reaction to take place, the difluoro complex being kinetically stable even at 60 degrees C.