Reactions of Mesityl Azide with Ferrocene‐Based N‐Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh<sub>2</sub>‐Functionalised Congeners
Robin Guthardt, Lisa Oetzel, Tobias Lang, Clemens Bruhn, Ulrich Siemeling
Abstract
Abstract The reactivity of ferrocene‐based N‐heterocyclic tetrylenes [{Fe(η 5 −C 5 H 4 −NSi t BuMe 2 ) 2 }E] (E=Ge, Sn, Pb) towards mesityl azide (MesN 3 ) is compared with that of PPh 2 ‐functionalised congeners exhibiting two possible reaction sites, namely the E II and P III atom. For E=Ge and Sn the reaction occurs at the E II atom, leading to the formation of N 2 and an E IV =NMes unit. The germanimines are sufficiently stable for isolation. The stannanimines furnish follow‐up products, either by [2+3] cycloaddition with MesN 3 or, in the PPh 2 ‐substituted case, by NMes transfer from the Sn IV to the P III atom. Whereas [{Fe(η 5 −C 5 H 4 −NSi t BuMe 2 ) 2 }Pb] and other diaminoplumbylenes studied are inert even under forcing conditions, the PPh 2 ‐substituted congener forms an addition product with MesN 3 , 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.