Inferring the Energetics of CO-Aniline Adduct Formation from Vibrational Spectroscopy.

Control of atmospheric CO is an important contemporary scientific and engineering challenge. Toward this goal, the reaction of CO with amines to form carbamate bonds is an established method for CO capture. However, controllable reversal of this reaction remains difficult and requires tuning the energetics of the carbamate bond. Through IR spectroscopy, we show that a characteristic frequency observed upon carbamate formation varies as a function of the substituent's Hammett parameter for a family of -substituted anilines. We present computational evidence that the vibrational frequency of the adducted CO serves as a predictor of the energy of formation of the carbamate. Electron donating groups typically enhance the driving force of carbamate formation by transferring more charge to the adducted CO and thus increasing the occupancy of the antibonding orbital in the carbon-oxygen bonds. Increased occupancy of the antibonding orbital within adducted CO indicates a weaker bond, leading to a red-shift in the characteristic carbamate frequency. Our work serves the large field of CO capture research where spectroscopic observables, such as IR frequencies, are more easily obtainable and can stand in as a descriptor of driving forces.