Exploration of the Mechanism of Platinum(II)-Catalyzed C–F Activation: Characterization and Reactivity of Platinum(IV) Fluoroaryl Complexes Relevant to Catalysis

Abstract

A series of Pt­(IV) complexes relevant to catalytic C–F activation have been prepared and structurally characterized. PtIV–F complexes, formed by C–F activation, underwent transmetalation with Me2Zn to generate Me3PtIV fluoroaryl complexes. In all cases, the Me3PtIV complex underwent reductive elimination to generate methylated organic products. The reactivity of both PtIV–F and Me3PtIV fluoroaryl complexes was strongly affected by the electronic nature of the cyclometalated fluoroaryl ligand.

Diverse Reactivity of Platinum SF3 and SF2 Complexes towards EtOH and Me3SiOEt

“…The value for the phosphorus–platinum coupling constant ( 1 J (P,Pt)=2948 Hz) is characteristic for a Pt II species . A triplet like pattern in the 19 F NMR at 233 K spectrum at δ =−278.5 ppm with corresponding 195 Pt satellites ( 1 J (F,Pt)=1128 Hz) can be assigned to the metal‐bound fluorido ligand (Figure ) –,,,. The chemical shift of the fluorido ligand in 5 is comparable to the one found for 2 .…”

Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes

“…The resonance for the latter appears at higher field at δ=−67.9 ppm as a triplet with Pt satellites ( 2 J F,Pt =297 Hz). The signal for the metal‐bound fluorido ligand is found as a singlet with Pt satellites ( 1 J F,Pt =227 Hz) at δ=−318.7 ppm, which is a typical chemical shift for transition metal bound fluorido ligands [1e,i,2h,3b,d,5a,6b,8d,11b,13d,15,20] . The two IMes ligands give one set of signals in the 1 H and 13 C{ 1 H} NMR spectra.…”

Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation, Fluoride Migration, and Hydrogen Bonding

“…[ 6d , 6i , 6m ] Love et al. demonstrated Pt( ii ) mediated C−F bond activation reactions generating Pt( iv ) fluorido complexes,[ 6b , 6c , 6e , 6f ] while Finze, Braunschweig and Bickelhaupt et al. presented the formation of a trifluorophosphane platinum( ii ) fluorido complex by P−F bond activation of PF 5 .…”