Activation of aromatic carbon-fluorine bonds by organoplatinum complexes

Diarylplatinum(II) Compounds as Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum Compounds with N-Donor Ligands

“…These reactions gave, in addition to cyclometallated platinum(II) and platinum(IV) compounds analogous to those described for the dimethylplatinum precursor, a new type of platinum(II) compound with a seven-membered metallacycle when X = Cl (Scheme 7). In agreement with previous results for the chemistry of dimethylplatinum analogues [41][42][43], a concerted mechanism is suggested for intramolecular C-X bond activation [61]; for X = Br a platinum(IV) compound is obtained at room temperature, while for X = H a platinum(II) compound is formed along with reductive elimination of benzene after refluxing in toluene the corresponding coordination compounds. Unexpectedly, under the conditions required for intramolecular activation of the C-Cl bond, a seven-membered metallacycle including a biaryl linkage is formed.…”

“…Thus, for electron-rich platinum precursors such as [PtMe 2 (dmso) 2 ] [31][32][33][34][35][36] or dimer [Pt 2 Me 4 (μ-SMe 2 ) 2 ] [37][38][39][40][41][42][43], the initial coordination of the ligand is followed by a cyclometallation step which, in this case, consists on oxidative addition followed by reductive elimination of methane. As shown in Scheme 1, in addition to formation of cyclometallated platinum(II) compounds, dimethylplatinum precursors allow formation of stable cyclometallated platinum(IV) compounds arising from intramolecular activation of C-X bonds (X = Cl, Br) [41][42][43] of adequately designed ligands. In recent years, several diarylplatinum(II) compounds containing labile ligands such as dimethylsulfoxide or dialkylsulfide have also been tested as metallating agents for N-donor ligands.…”

Pentafluorobenzaldehyde and its utilizing in organic synthesis

“…The pentafluorobenzaldehyde when treated the toluenesulfonamide yields 79% N-tosyl-pentafluorobenzylidene amine (Scheme 43 [501][502][503]). …”

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

“…Although a number of high oxidation state alkylmetal fluorides were reported in the twentieth century [41,42], they apparently were not reactive toward C(sp (Fig. 15) [43].…”