Protonation of (N-N)PtPh2 (1; N-N = diimine ArN=CMe-CMe=NAr with Ar = 2,6-Me2C6H3 (a), 2,4,6-Me3C6H2 (b), 4-Br-2,6-Me2C6H2 (C), 3,5-Me2C6H3 (d), and 4-CF3C6H4 (e)) in the presence of MeCN at ambient temperature generates (N-N)Pt(Ph)(NCMe)(+) (2). At -78 degrees C, protonation of 1a yielded (N-N)PtPh2(H)(NCMe)(+) (3a), which produced benzene and 2a at ca. -40 degrees C. Protonation of 1a-e in CD2Cl2/Et2O-d(10) furnished (N-N)Pt(C6H5)(eta(2)-C6H6)(+) (4a-e). The pi-benzene complexes 4a-c, sterically protected at Pt, eliminate benzene at ca. 0 degrees C. The sterically less protected 4d-e lose benzene already at -30 degrees C. SST and 2D EXSY NMR demonstrate that phenyl and T-benzene ligand protons undergo exchange with concomitant symmetrization of the diimine ligand, most likely via oxidative insertion of Pt into a C-H bond of coordinated benzene. The kinetics of the exchange processes for 4a-c were probed by quantitative EXSY spectroscopy, resulting in Delta H-double dagger of 70-72 kJ mol(-1) and Delta S-double dagger of 37-48 J K-1 mol(-1). A large, strongly temperature-dependent H/D kinetic isotope effect (9.7 at -34 degrees C; 6.9 at -19 degrees C) was measured for the dynamic behavior of 4a versus 4a-d(10), consistent with the proposed pi-benzene C-H bond cleavage. The fact that the pi-benzene complex 4a is thermally more robust in the absence of MeCN than is the Pt(IV) hydridodiphenyl complex 3a in the presence of MeCN agrees with the notion that arene elimination from Pt(IV) hydridoaryl complexes occurs via Pt(II) pi-arene intermediates that eliminate the hydrocarbon associatively, in this case, promoted by MeCN. Compounds 1a, 1b, 1d, 2a, and 2b have been crystallographically characterized.