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Reactions of Mesityl Azide with Ferrocene‐Based N‐Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh(2)‐Functionalised Congeners

The reactivity of ferrocene‐based N‐heterocyclic tetrylenes [{Fe(η(5)−C(5)H(4)−NSitBuMe(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 reac...

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Detalles Bibliográficos
Autores principales: Guthardt, Robin, Oetzel, Lisa, Lang, Tobias, Bruhn, Clemens, Siemeling, Ulrich
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400874/
https://www.ncbi.nlm.nih.gov/pubmed/35510599
http://dx.doi.org/10.1002/chem.202200996
Descripción
Sumario:The reactivity of ferrocene‐based N‐heterocyclic tetrylenes [{Fe(η(5)−C(5)H(4)−NSitBuMe(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)−NSitBuMe(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.