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2020-10-15Author
Weyer, NadineHeinz, MyronSchweizer, Julia IsabellaBruhn, ClemensHolthausen, Max C.Siemeling, UlrichMetadata
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Aufsatz
A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone
Abstract
The N-heterocyclic silylene [{Fe(η⁵-C₅H4-NDipp)₂}Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO₂ and N₂O, respectively affording (1DippSiO₂)₂C and (1DippSiO)₂ as follow-up products of the silanone 1DippSiO. Its reactions with H₂O, NH₃, and FcPH₂ (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH₂, PHFc). Its reaction with H₃BNH₃ unexpectedly results in B−H, instead of N−H, bond activation, affording 1DippSi(H)(BH₂NH₃). DFT results suggest that dramatically different mechanisms are operative for these H−X insertions.
Citation
In: Angewandte Chemie Volume 60 / Issue 5 (2020-10-15) , S. 2624-2628 ; eissn:1521-3773Sponsorship
Gefördert im Rahmen des Projekts DEALCitation
@article{doi:10.17170/kobra-202107204382,
author={Weyer, Nadine and Heinz, Myron and Schweizer, Julia Isabella and Bruhn, Clemens and Holthausen, Max C. and Siemeling, Ulrich},
title={A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone},
journal={Angewandte Chemie},
year={2020}
}
0500 Oax 0501 Text $btxt$2rdacontent 0502 Computermedien $bc$2rdacarrier 1100 2020$n2020 1500 1/eng 2050 ##0##http://hdl.handle.net/123456789/13197 3000 Weyer, Nadine 3010 Heinz, Myron 3010 Schweizer, Julia Isabella 3010 Bruhn, Clemens 3010 Holthausen, Max C. 3010 Siemeling, Ulrich 4000 A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone / Weyer, Nadine 4030 4060 Online-Ressource 4085 ##0##=u http://nbn-resolving.de/http://hdl.handle.net/123456789/13197=x R 4204 \$dAufsatz 4170 5550 {{Carbene}} 5550 {{Einschiebungsreaktion}} 5550 {{Metallocene}} 5550 {{Silicium}} 5550 {{Valenz <Chemie>}} 7136 ##0##http://hdl.handle.net/123456789/13197
2021-09-01T11:11:32Z 2021-09-01T11:11:32Z 2020-10-15 doi:10.17170/kobra-202107204382 http://hdl.handle.net/123456789/13197 Gefördert im Rahmen des Projekts DEAL eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ carbene homologues insertion metallocenes silicon subvalent compounds 540 A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone Aufsatz The N-heterocyclic silylene [{Fe(η⁵-C₅H4-NDipp)₂}Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO₂ and N₂O, respectively affording (1DippSiO₂)₂C and (1DippSiO)₂ as follow-up products of the silanone 1DippSiO. Its reactions with H₂O, NH₃, and FcPH₂ (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH₂, PHFc). Its reaction with H₃BNH₃ unexpectedly results in B−H, instead of N−H, bond activation, affording 1DippSi(H)(BH₂NH₃). DFT results suggest that dramatically different mechanisms are operative for these H−X insertions. open access Weyer, Nadine Heinz, Myron Schweizer, Julia Isabella Bruhn, Clemens Holthausen, Max C. Siemeling, Ulrich doi:10.1002/anie.202011691 Carbene Einschiebungsreaktion Metallocene Silicium Valenz <Chemie> publishedVersion eissn:1521-3773 Issue 5 Angewandte Chemie 2624-2628 Volume 60 false
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