Electronic Structure of RhO, Its Ammoniated Complexes (NH)RhO, and Mechanistic Exploration of CH Activation by Them.

High-level electronic structure calculations are initially performed to investigate the electronic structure of RhO. The construction of potential energy curves for the ground and low-lying excited states allowed the calculation of spectroscopic constants, including harmonic and anharmonic vibrational frequencies, bond lengths, spin-orbit constants, and excitation energies. The equilibrium electronic configurations were used for the interpretation of the chemical bonding. We further monitored how the Rh-O bonding scheme changes with the gradual addition of ammonia ligands. The nature of this bond remains unaffected up to four ammonia ligands but adopts a different electronic configuration in the pseudo-octahedral geometry of (NH)RhO. This has consequences in the activation mechanism of the C-H bond of methane by these complexes, especially (NH)RhO. We show that the [2 + 2] mechanism in the (NH)RhO case has a very low energy barrier comparable to that of a radical mechanism. We also demonstrate that methane can coordinate to the metal in a similar fashion to ammonia and that knowledge of the electronic structure of the pure ammonia complexes provides qualitative insights into the optimal reaction mechanism.