Experiments and Direct Dynamics Simulations That Probe η2-Arene/Aryl Hydride Equilibria of Tungsten Benzene Complexes.

Key steps in the functionalization of an unactivated arene often involve its dihaptocoordination by a transition metal followed by insertion into the C-H bond. However, rarely are the η2-arene and aryl hydride species in measurable equilibrium. In this study, the benzene/phenyl hydride equilibrium is explored for the {WTp(NO)(PBu3)} (Bu = n-butyl; Tp = trispyrazoylborate) system as a function of temperature, solvent, ancillary ligand, and arene substituent. Both face-flip and ring-walk isomerizations are identified through spin-saturation exchange measurements, which both appear to operate through scission of a C-H bond. The effect of either an electron-donating or electron-withdrawing substituent is to increase the stability of both arene and aryl hydride isomers. Crystal structures, electrochemical measurements, and extensive NMR data further support these findings. Static density functional theory calculations of the benzene-to-phenyl hydride landscape suggest a single linear sequence for this transformation involving a sigma complex and oxidative cleavage transition state. Static DFT calculations also identified an η2-coordinated benzene complex in which the arene is held more loosely than in the ground state, primarily through dispersion forces. Although a single reaction pathway was identified by static calculations, quasiclassical direct dynamics simulations identified a network of several reaction pathways connecting the η2-benzene and phenyl hydride isomers, due to the relatively flat energy landscape.