Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d-electron counts are of interest. A series of terminal Mo nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo nitrido complex, an early metal nitride with four valence d-electrons. The binding mode of the para-terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M-N bond order of three. Even with an intact Mo≡N bond, this low-valent nitrido complex proves to be highly reactive, readily undergoing N-atom transfer upon addition of CO, releasing cyanate anion.
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Synthesis and electrochemical properties of molybdenum nitrido complexes supported by redox-active NHC and MIC ligands.
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