Date
2022-05-05Subject
540 Chemistry AzideChemische SyntheseEisenkomplexeChemische ReaktionStaudinger-ReaktionCarbeneMetadata
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Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh₂-Functionalised Congeners
Abstract
The active PbII/P Lewis pair nature of a PPh₂-functionalised ferrocene-based N-heterocyclic plumbylene is demonstrated by its reaction with mesityl azide to afford a phosphazide, which is in contrast to the inertness of the unfunctionalised congener. The lighter analogues most likely react with MesN₃ at their respective tetrel atom Eᴵᴵ, leading to the formation of N₂ and an Eᶦᵛ=NMes unit, followed by NMes transfer from the Eᶦᵛ to the Pᴵᴵᴵ atom.
The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η⁵−C₅H₄−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 Eᶦᵛ=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 Snᶦᵛ to the Pᴵᴵᴵ atom. Whereas [{Fe(η⁵−C₅H₄−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.
The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η⁵−C₅H₄−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 Eᶦᵛ=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 Snᶦᵛ to the Pᴵᴵᴵ atom. Whereas [{Fe(η⁵−C₅H₄−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.
Citation
In: Chemistry - a European journal Volume 28 / Issue 42 (2022-05-05) eissn:1521-3765Sponsorship
Gefördert im Rahmen des Projekts DEALCitation
@article{doi:10.17170/kobra-202207286541,
author={Guthardt, Robin and Oetzel, Lisa and Lang, Tobias and Bruhn, Clemens and Siemeling, Ulrich},
title={Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh₂-Functionalised Congeners},
journal={Chemistry - a European journal},
year={2022}
}
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2022-08-11T13:11:33Z 2022-08-11T13:11:33Z 2022-05-05 doi:10.17170/kobra-202207286541 http://hdl.handle.net/123456789/14046 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ azides carbene homologues metallocenes subvalent compounds tetrylenes 540 Reactions of Mesityl Azide with Ferrocene-Based N-Heterocyclic Germylenes, Stannylenes and Plumbylenes, Including PPh₂-Functionalised Congeners Aufsatz The active PbII/P Lewis pair nature of a PPh₂-functionalised ferrocene-based N-heterocyclic plumbylene is demonstrated by its reaction with mesityl azide to afford a phosphazide, which is in contrast to the inertness of the unfunctionalised congener. The lighter analogues most likely react with MesN₃ at their respective tetrel atom Eᴵᴵ, leading to the formation of N₂ and an Eᶦᵛ=NMes unit, followed by NMes transfer from the Eᶦᵛ to the Pᴵᴵᴵ atom. The reactivity of ferrocene-based N-heterocyclic tetrylenes [{Fe(η⁵−C₅H₄−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 Eᶦᵛ=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 Snᶦᵛ to the Pᴵᴵᴵ atom. Whereas [{Fe(η⁵−C₅H₄−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. open access Guthardt, Robin Oetzel, Lisa Lang, Tobias Bruhn, Clemens Siemeling, Ulrich doi:10.1002/chem.202200996 Azide Chemische Synthese Eisenkomplexe Chemische Reaktion Staudinger-Reaktion Carbene publishedVersion eissn:1521-3765 Issue 42 Chemistry - a European journal Volume 28 false
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