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The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N 3 ) 3 ], [MoO(N 3 ) 3 ⋅2 CH 3 CN], [(bipy)MoO(N 3 ) 3 ], [MoO(N 3 ) 5 ] 2− , [WO(N 3 ) 4 ], and [WO(N 3 ) 4 ⋅CH 3 CN]
Author(s) -
Haiges Ralf,
Skotnitzki Juri,
Fang Zongtang,
Dixon David A.,
Christe Karl O.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201505418
Subject(s) - molybdenum , tungsten , tungsten compounds , crystallography , materials science , inorganic chemistry , chemistry , metallurgy
A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF 4 ] (M=Mo, W) and Me 3 SiN 3 . While [WO(N 3 ) 4 ] was formed through fluoride–azide exchange in the reaction of Me 3 SiN 3 with WOF 4 in SO 2 solution, the reaction with MoOF 4 resulted in a reduction of Mo VI to Mo V and formation of [MoO(N 3 ) 3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N 3 ) 3 ⋅2 CH 3 CN] and [WO(N 3 ) 4 ⋅CH 3 CN]. Subsequent reactions of [MoO(N 3 ) 3 ] with 2,2′‐bipyridine and [PPh 4 ][N 3 ] resulted in the formation and isolation of [(bipy)MoO(N 3 ) 3 ] and [PPh 4 ] 2 [MoO(N 3 ) 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(N 3 ) 4 ⋅CH 3 CN], [(bipy)MoO(N 3 ) 3 ], and [PPh 4 ] 2 [MoO(N 3 ) 5 ], by their X‐ray crystal structures.