Electron-transfer reactions in nitrogen fixation. Part 1. The electrosynthesis of dinitrogen, hydride, isocyanide, and carbonyl complexes of molybdenum: intermediates, mechanisms, and energetics

Abstract

Dinitrogen, hydride, carbonyl, and isocyanide complexes of Mo⁰ and W⁰ can be electrosynthesised from the molecular substrates N₂, H₂, etc. and precursors trans-[MX₂(Ph₂PCH₂CH₂PPh₂)₂](M = MO; X = Cl, Br, I, SPh, or SBuⁿ; M = W; X = Cl), [MoH₂Cl₂(Ph₂PCH₂CH₂PPh₂)₂], or from MoCl₅ and Ph₂PCH₂CH₂PPh₂. Intermediates, mechanisms, and energetics associated with the electrosyntheses are described.