Aufsatz
Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4
Abstract
The stable ferrocene-based N-heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1’-ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6-diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC�CH, and RC�CR (R=Ph, SiMe3). The Dippsubstituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2-diazaborolylsubstituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head-to-tail dimer.
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Gefördert im Rahmen des Projekts DEALCitation
@article{doi:10.17170/kobra-2024080210631,
author={Jacob, Hannes Lukas and Weyer, Nadine and Leibold, Michael and Bruhn, Clemens and Siemeling, Ulrich},
title={Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4},
journal={Chemistry - A European Journal},
year={2024}
}
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3010 Leibold, Michael
3010 Bruhn, Clemens
3010 Siemeling, Ulrich
4000 Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4 / Jacob, Hannes Lukas
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5550 {{Carbene}}
5550 {{Eisen}}
5550 {{Silicium}}
5550 {{Silane}}
5550 {{Einschiebungsreaktion}}
5550 {{Heterocyclische Verbindungen}}
7136 ##0##http://hdl.handle.net/123456789/15955
<resource xsi:schemaLocation="http://datacite.org/schema/kernel-2.2 http://schema.datacite.org/meta/kernel-2.2/metadata.xsd"> 2024-08-02T12:15:55Z 2024-08-02T12:15:55Z 2024-06-07 doi:10.17170/kobra-2024080210631 http://hdl.handle.net/123456789/15955 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ Carbene homologues Chalcogens Metallocenes Silicon Subvalent compounds 540 Ferrocene-Based N-Heterocyclic Silylenes: Monomeric Silanechalcogenones, Silanimines, Silirenes, and Insertion Products with P4 Aufsatz The stable ferrocene-based N-heterocyclic silylenes fc[(N{B})2Si] (A; fc=1,1’-ferrocenylene, {B}=(HCNDipp)2B, Dipp=2,6-diisopropylphenyl) and fc[(NDipp)2Si] (B) are compared in a study focussing on their reactivity towards a range of small to moderately sized molecular substrates, viz. P4, S8, Se8, MesN3 (Mes=mesityl), RC�CH, and RC�CR (R=Ph, SiMe3). The Dippsubstituted congener B exhibits a more pronounced ambiphilicity and is sterically less congested than its 1,3,2-diazaborolylsubstituted relative A, in line with the higher reactivity of the former. The difference in reactivity is obviously due more to electronic than to steric reasons, as is illustrated by the fact that both A and B react with the comparatively bulky substrate MesN3 under mild conditions to afford the corresponding silanimine fc[(N{B})2Si=NMes] and fc[(NDipp)2Si=NMes], respectively. The heavier ketone analogues fc[(N{B})2Si=E] (E=S, Se, Te) are readily available from A and the corresponding chalcogen. In contrast, the reaction of the more reactive silylene B with elemental sulfur or selenium is unspecific, affording product mixtures. However, fc[(NDipp)2Si=Se] is selectively prepared from B and (Et2N)3PSe; the Te analogue is also accessible, but crystallises as head-to-tail dimer. open access Jacob, Hannes Lukas Weyer, Nadine Leibold, Michael Bruhn, Clemens Siemeling, Ulrich doi:10.1002/chem.202400850 Carbene Eisen Silicium Silane Einschiebungsreaktion Heterocyclische Verbindungen publishedVersion eissn:1521-3765 Issue 36 Chemistry - A European Journal Volume 30 false e202400850 </resource>
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