The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N-3)(2), MO2(N-3)(2)center dot 2CH(3)CN, (bipy)MO2(N-3)(2), and [MO2(N-3)(4)](2-) (M=Mo, W)

摘要

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N-3)(2) (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N-3)(2)2CH(3)CN. The subsequent reaction of MO2(N-3)(2) with 2,2-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N-3)(2). The hydrolysis of (bipy)MoO2(N-3)(2) resulted in the formation and isolation of [(bipy)MoO2N3](2)O. The tetraazido anions [MO2(N-3)(4)](2-) were obtained by the reaction of MO2(N-3)(2) with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N-3)(2), (bipy)WO2(N-3)(2), [PPh4](2)[MoO2(N-3)(4)], [PPh4](2)[WO2(N-3)(4)], and [(bipy)MoO2N3](2)O by their X-ray crystal structures.