摘要
Reactions of organic azides RN 3 with two univalent inverted-sandwich complexes (μ-η 6 :η 6 -C 6 H 5 CH 3 )[M(Nacnac)] 2 (M = Cr (1) and V (2); Nacnac = HC(C(Me)NC 6 H 3 i Pr 2 ) 2 ) have been investigated. Where R = p-tolyl, reaction with 1 results in reductive N 2 elimination and the formation of a diimido product Cr(NR) 2 (Nacnac) and a cycloaddition tetrazene product Cr[N(R)NNN(R)](Nacnac), which can be converted to Cr(NR) 2 (Nacnac) upon thermolysis. However, reaction of 1 with Me 3 SiN 3 does not produce a diimido complex, but a monomeric three-coordinate amido product Cr[N(SiMe 3 ) 2 ](Nacnac) and an azide-bridged dinuclear compound [Cr(μ-N 3 )(Nacnac)] 2 . On the other hand, where R = p-tolyl, 1-adamantyl, or SiMe 3 , reaction with the more reducing 2 gives solely a diimido product V(NR) 2 (Nacnac). The symmetric diimido complex V(NSiMe 3 ) 2 (Nacnac) (10) can be converted to an asymmetric diimido complex V(NSiMe 3 )(N-2,6-C 6 H 3 i Pr 2 )[Me 3 SiNC(Me)C(H)C(Me)N(2,6- C 6 H 3 i Pr 2 )] (11) upon heating. © 2010 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.