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 -C H -NSitBuMe ) }E] (E=Ge, Sn, Pb) towards mesityl azide (MesN ) is compared with that of PPh -functionalised congeners exhibiting two possible reaction sites, namely the E and P atom. For E=Ge and Sn the reaction occurs at the E at...

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Published inChemistry : a European journal Vol. 28; no. 42; p. e202200996
Main Authors Guthardt, Robin, Oetzel, Lisa, Lang, Tobias, Bruhn, Clemens, Siemeling, Ulrich
Format Journal Article
LanguageEnglish
Published Germany 26.07.2022
Subjects
Azides
Coordination Complexes
Lead
Metallocenes
Models, Molecular
tetrylenes
Azides
carbene homologues
subvalent compounds
metallocenes
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Summary:The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η -C H -NSitBuMe ) }E] (E=Ge, Sn, Pb) towards mesityl azide (MesN ) is compared with that of PPh -functionalised congeners exhibiting two possible reaction sites, namely the E and P atom. For E=Ge and Sn the reaction occurs at the E atom, leading to the formation of N and an E =NMes unit. The germanimines are sufficiently stable for isolation. The stannanimines furnish follow-up products, either by [2+3] cycloaddition with MesN or, in the PPh -substituted case, by NMes transfer from the Sn to the P atom. Whereas [{Fe(η -C H -NSitBuMe ) }Pb] and other diaminoplumbylenes studied are inert even under forcing conditions, the PPh -substituted congener forms an addition product with MesN , 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.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202200996