Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1661 (USA).
Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487 (USA).
Angew Chem Int Ed Engl. 2015 Dec 14;54(51):15550-5. doi: 10.1002/anie.201505418. Epub 2015 Nov 2.
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.
一系列新型的钼（V）和钨（VI）氧化氮配合物是由[MOF4]（M=Mo，W）和 Me3SiN3 开始制备的。当 Me3SiN3 与 WOF4 在 SO2 溶液中反应时，通过氟化物-叠氮化物交换形成[WO（N3）4]，而与 MoOF4 的反应导致 Mo（VI）还原为 Mo（V）并形成[MoO（N3）3]。在乙腈溶液中进行这些反应，导致相应的加合物[MoO（N3）3·2CH3CN]和[WO（N3）4·CH3CN]被分离出来。随后，[MoO（N3）3]与 2,2'-联吡啶和[PPh4][N3]的反应分别导致[(bipy)MoO（N3）3]和[PPh4]2[MoO（N3）5]的形成和分离。大多数钼（V）和钨（VI）氧化氮配合物通过其振动光谱、撞击、摩擦和热灵敏度数据进行了充分的表征，在[WO（N3）4·CH3CN]、[(bipy)MoO（N3）3]和[PPh4]2[MoO（N3）5]的情况下，还通过其 X 射线晶体结构进行了表征。
