A Versatile Comproportionation Route to Construct Mono-Imido Trichlorido Complexes of Molybdenum(V) and Tungsten(V)

We report the facile and high-yielding multi-gram synthesis of pentavalent heavy group VI mono-imido complexes with the general formula M(NR)Cl3Ln (M=Mo, W, R=Aryl or Alkyl, L=DME n=1 or Py n=2) following a comproportionative imido group transfer procedure starting from the corresponding bis-imido complexes and MCl4. The procedure works well for both aryl and alkyl imido ligands, in the case of molybdenum but only for alkyl imidos in the case of tungsten. Overall, five mono-imido complexes have been structurally characterized and purity is established by elemental analysis and EPR spectroscopy. image