The df-d Dative Bonding in a Uranium-Cobalt Heterobimetallic Complex for Efficient Nitrogen Fixation

Single transition-metal site catalysts with s-, p-, or d-block atom anchor for nitrogen fixation have been extensively studied, and yet the studies of the f-block atom anchor are rarely reported. Thus, we investigate the feasibility of using a newly synthesized U-Co complex featuring a single Co^I site coordinated by tetrakis(phophinoamide) and an U^IV anchor for N₂-to-NH₃ conversion by theoretical modeling. We characterize the evolution of oxidation states of U and Co along the reaction pathways from ab initio density matrix renormalization group (DMRG) calculations, and we find that the variation of the Co → U dative bond is correlated with the changes of oxidation states. Both uranium and cobalt can serve as electron reservoirs to facilitate breaking the N-N bond. Our study demonstrates the viability of metal → metal dative bonds, particularly the df-d one, for the reduction of N₂ to NH₃, and thus, this opens up a new avenue to the rational design of efficient catalyst for nitrogen fixation.