Dinitrogen functionalization under ambient conditions remains a challenge in the field of catalytic chemistry. Structures baring transitional metal center(s) have displayed interesting reactivities and have been suggested for the catalytic conversion of dinitrogen to ammonia. Using molybdenum, one of the most azophilic metals of the transitional metal series, moderate ammonia yields have been attained. Although much effort has been expanded in the topic of N2 fixation, relevant questions still require addressing with regards to the chemical activity that takes place during the nitrogen reduction process under different ligand field environments. Here, we present a density functional theory study of the ligand field effect on the ground and redox states of MoN2 species baring multiple strength ligands. Multiconfigurational complete-active space self-consistent field (CASSCF) method and its second-order perturbative complement (CASPT2) methodologies were applied in order to enhance the accuracy of the study. This study will shed light on the electronic structure and binding properties of molybdenum based molecular systems. In addition, the understanding of the reactivity of known catalytically active complexes will provide insight into the development and improvement of novel synthetic catalysts.

Ligand field effects on the N2 activation by molybdenum

ACS Spring 2022

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