Heterobimetallic dinitrogen complexes that contain the {[N3N]Mo-N=N)(-) ligand

{[N3N]Mo-N=N}(2)Mg(THF)(2) reacts with FeCl2 at -20 degrees C in a mixture of ether, THF, and toluene to yield paramagnetic {[N3N]Mo-N=N}(3)Fe (1), an X-ray study of which shows it to contain iron in a trigonal planar environ ment. X-band ESR, iron-57 Mossbauer spectroscopy, and magnetic susceptibili ty studies of 1 confirm that it contains high-spin Fe(III) in an anisotropi c magnetic environment. Addition of DMPE to toluene solutions of 1 results in loss of [N3N]MoN2 from the coordination sphere to give {[N3N]Mo-N=N}(2)F e(DMPE) (2). SQUID magnetic susceptibility and Mossbauer data are in accord with formulation of 2 as a high-spin Fe(II) complex. {[N3N]Mo-N=N}(2)Mg(TH F)(2) reacts with VCl4(DME) and VCl3(THF)(3) in THF to give paramagnetic {[ N3N]Mo-N=N}(3)VCl (3) in 28-42% yield. A second paramagnetic complex is als o produced in these reactions and has been identified by X-ray crystallogra phy as {[N3N]Mo-N=N)(2)VCl(THF) (4). Several zirconium/molybdenum dinitroge n complexes have been prepared by the reaction between {[N3N]Mo-N=N})(2)Mg( THF)(2) and ZrCl4(THF)(2), and {[N3N]Mo-N=N}(2)ZrCl2 has been characterized by X-ray crystallography.