Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh2 -Functionalised Congeners.

The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η5 -C5 H4 -NSitBuMe2 )2 }E] (E=Ge, Sn, Pb) towards mesityl azide (MesN3 ) is compared with that of PPh2 -functionalised congeners exhibiting two possible reaction sites, namely the EII and PIII atom. For E=Ge and Sn the reaction occurs at the EII atom, leading to the formation of N2 and an EIV =NMes unit. The germanimines are sufficiently stable for isolation. The stannanimines furnish follow-up products, either by [2+3] cycloaddition with MesN3 or, in the PPh2 -substituted case, by NMes transfer from the SnIV to the PIII atom. Whereas [{Fe(η5 -C5 H4 -NSitBuMe2 )2 }Pb] and other diaminoplumbylenes studied are inert even under forcing conditions, the PPh2 -substituted congener forms an addition product with MesN3 , thus showing a behaviour similar to that of frustrated Lewis pairs. The germylenes of this study afford copper(I) complexes with CuCl, including the first structurally characterised linear dicoordinate halogenido complex [CuX(L)] with a heavier tetrylene ligand L.