Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant aminesElectronic supplementary information (ESI) available: X-ray crystallographic data and experimentals, NMR and IR electrochemical data. CCDC reference numbers 854188854202 and 863033. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt12224c

Molybdenum and tungsten bis(dinitrogen) complexes of the formula M(N 2 ) 2 (PNP) 2 (M = Mo and W) and W(N 2 ) 2 (dppe)(PNP), supported by diphosphine ligands containing a pendant amine of the formula (CH 2 PR 2 ) 2 NR = P R N R P R (R = Et, Ph; R = Me, Bn), have been prepared by Mg reduction of metal halides under an N 2 atmosphere. The complexes have been characterized by NMR and IR spectroscopy, X-ray crystallography, and cyclic voltammetry. Reactivity of the target Mo and W bis(dinitrogen) compounds with CO results in the formation of dicarbonyl complexes. Molybdenum and tungsten bis(dinitrogen) complexes, incorporating pendant amine ligands, have been prepared and characterized by NMR and IR spectroscopy, X-ray crystallography, and electrochemical methods.