Halide Effects in Reductive Splitting of Dinitrogen with Rhenium Pincer Complexes

Transition metal halide complexes are used as precursors for reductive N₂ activation up to full splitting into nitride complexes. Distinct halide effects on the redox properties and yields are frequently observed yet not well understood. Here, an electrochemical and computational examination of reductive N₂ splitting with the rhenium(III) complexes [ReX₂(PNP)] (PNP = N(CH₂CH₂PtBu₂)₂ and X = Cl, Br, I) is presented. As previously reported for the chloride precursor ( J. Am. Chem. Soc.2018, 140, 7922), the heavier halides give rhenium(V) nitrides upon (electro-)chemical reduction in good yields yet with significantly anodically shifted electrolysis potentials along the halide series. Dinuclear, end-on N₂-bridged complexes, [{ReX(PNP)}₂(μ-N₂)], were identified as key intermediates in all cases. However, while the chloride complex is exclusively formed via 2-electron reduction and Re^III/Re^I comproportionation, the iodide system also reacts via an alternative Re^II/Re^II-dimerization mechanism at less negative potentials. This alternative pathway relies on the absence of the potential inversion after reduction and N₂ activation that was observed for the chloride precursor. Computational analysis of the relevant Re^III/II and Re^II/I redox couples by energy decomposition analysis attributes the halide-induced trends of the potentials to the dominating electrostatic Re-X bonding interactions over contributions from charge transfer.