title: The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].
abstract: A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures.
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1661 (USA). haiges@usc.edu.
authors.forename: Ralf
authors.initials: R
authors.lastname: Haiges
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1661 (USA).
authors.forename: Juri
authors.initials: J
authors.lastname: Skotnitzki
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487 (USA).
authors.forename: Zongtang
authors.initials: Z
authors.lastname: Fang
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487 (USA).
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1661 (USA).
authors.forename: Karl O
authors.initials: KO
authors.lastname: Christe
keywords: crystal structures; molybdenum; oxoazides; polyazides; tungsten