Small, Electron-Donating Substituents Give CO 2 Activation by Permethylpentalene Zirconium Amido Complexes the Upper Hand: A DFT Study of Distortion and Interaction.

An insight into factors controlling CO 2 activation is necessary to develop molecular systems that utilize CO 2 as a chemical feedstock. Two permethylpentalene zirconium cyclopentadienyl (mono)amido complexes, Pn*ZrCp(NR 2 ), were previously assessed for CO 2 activation, and a strong dependence on the amido substituent was observed. The R = Me analogue reacted rapidly and quantitatively at room temperature to form the carbamato complex, while the R = Ph species was inert. Here, we investigate the origin of this reactivity difference using DFT and the distortion-interaction model to characterize steric and electronic contributions to the activation barrier. We find that the barrier for CO 2 insertion with R = Me (19.1 kcal/mol) is lower than with R = Ph (36.6 kcal/mol), explaining the inertness of the Ph-substituted analogue. The distortion energy trend follows the steric bulk of the amido substituents, and the bulkier Ph-substituted complex has a consistently higher distortion energy along its potential energy surface than that of the Me-substituted complex. The interaction energy trend follows the electronics, and a more electron-donating Me-substituted complex shows a consistently lower interaction energy. The balance of these effects at the corresponding TS gives a reduced activation barrier. Small, electron-donating substituents therefore facilitate CO 2 activation in these complexes.