Preparation of the first manganese(III) and manganese(IV) azides.

Ralf Haiges, Robert J Buszek, Jerry A Boatz, Karl O Christe

Index: Angew. Chem. Int. Ed. Engl. 53(31) , 8200-5, (2014)

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Abstract

Fluoride-azide exchange reactions of Me3SiN3 with MnF2 and MnF3 in acetonitrile resulted in the isolation of Mn(N3)2 and Mn(N3)3 ⋅CH3CN, respectively. While Mn(N3)2 forms [PPh4]2[Mn(N3)4] and (bipy)2Mn(N3)2 upon reaction with PPh4N3 and 2,2'-bipyridine (bipy), respectively, the manganese(III) azide undergoes disproportionation and forms mixtures of [PPh4]2[Mn(N3)4] and [PPh4]2[Mn(N3)6], as well as (bipy)2Mn(N3)2 and (bipy)Mn(N3)4. Neat and highly sensitive Cs2[Mn(N3)6] was obtained through the reaction of Cs2MnF6 with Me3SiN3 in CH3CN.© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.