Adding a New Dimension to the Investigation of Platinum-Mediated Arene C−H Activation Reactions Using 2D NMR Exchange Spectroscopy. Dynamics of Pt(II) Phenyl/Benzene Site Exchange

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 °C, protonation of 1a yielded (N−N)PtPh2(H)(NCMe)+ (3a), which produced benzene and 2a at ca. −40 °C. Protonation of 1a−e in CD2Cl2/Et2O-d10 furnished (N−N)Pt(C6H5)(η2−C6H6)+ (4a−e). The π-benzene complexes 4a−c, sterically
protected at Pt, eliminate benzene at ca. 0 °C. The sterically less protected 4d−e lose benzene already at
−30 °C. SST and 2D EXSY NMR demonstrate that phenyl and π-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 ΔH⧧ of 70−72 kJ mol-1 and ΔS⧧ of 37−48 J K-1 mol-1. A large, strongly
temperature-dependent H/D kinetic isotope effect (9.7 at −34 °C; 6.9 at −19 °C) was measured for the
dynamic behavior of 4a versus 4a-d10, consistent with the proposed π-benzene C−H bond cleavage. The
fact that the π-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) π-arene intermediates that eliminate the hydrocarbon
associatively, in this case, promoted by MeCN. Compounds 1a, 1b, 1d, 2a, and 2b have been
crystallographically characterized.