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The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO 2 (N 3 ) 2 , MO 2 (N 3 ) 2 ⋅2 CH 3 CN, (bipy)MO 2 (N 3 ) 2 , and [MO 2 (N 3 ) 4 ] 2− (M=Mo, W)
Author(s) -
Haiges Ralf,
Skotnitzki Juri,
Fang Zongtang,
Dixon David A.,
Christe Karl O.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504629
Subject(s) - molybdenum , chemistry , adduct , tungsten , azide , acetonitrile , bipyridine , fluoride , thiocyanate , crystal structure , ionic bonding , tungstate , inorganic chemistry , medicinal chemistry , crystallography , ion , organic chemistry
Molybdenum(VI) and tungsten(VI) dioxodiazide, MO 2 (N 3 ) 2 (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO 2 F 2 and Me 3 SiN 3 in SO 2 solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO 2 (N 3 ) 2 ⋅2 CH 3 CN. The subsequent reaction of MO 2 (N 3 ) 2 with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO 2 (N 3 ) 2 . The hydrolysis of (bipy)MoO 2 (N 3 ) 2 resulted in the formation and isolation of [(bipy)MoO 2 N 3 ] 2 O. The tetraazido anions [MO 2 (N 3 ) 4 ] 2− were obtained by the reaction of MO 2 (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)MoO 2 (N 3 ) 2 , (bipy)WO 2 (N 3 ) 2 , [PPh 4 ] 2 [MoO 2 (N 3 ) 4 ], [PPh 4 ] 2 [WO 2 (N 3 ) 4 ], and [(bipy)MoO 2 N 3 ] 2 O by their X‐ray crystal structures.