Anhydrous cationic Pt(II) complexes [(NN)Pt(CH_3)(CF_3CD_2OD)]+ (1, NN = ArNC(Me)−C(Me)NAr), which are obtained by reaction of (NN)Pt(CH_3)_2 with B(C_6F_5)_3 in CF_3CD_2OD, activate C−H bonds of benzene and methylbenzenes, with enhanced reactivity compared to the previously prepared equilibrium mixtures with the (thermodynamically favored) aquo complexes. For methylbenzenes (toluene, p-xylene, mesitylene), activation at the aromatic and benzylic positions are kinetically competitive, but the product of the latter is strongly favored thermodynamically. This unusual trend is attributed to formation of η^3-benzyl structures, which can be observed spectroscopically for 1,4-diethylbenzene activation
