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Abstract Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal MoIVnitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first MoIInitrido 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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Transition metal phosphide films were synthesized using a mild electrochemical method. Dibenzo-7-phosphanorbornadiene derivatives (XPA) are introduced as versatile precursors to amorphous metal phosphide electrocatalysts for proton reduction in acidic water. Homogeneous model reactions reveal distinct reactivity between XPA and nickel in different oxidation states, with Ni(0) resulting in Ni x P y formation.more » « less
