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 °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 °C.