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A cyclopentadienyl functionalized silylene-a flexible ligand for Si- And C-coordination

Kaufmann, S. 1; Krätschmer, F. 1; Köppe, R. 1; Schon, T. 1; Schoo, C. 1; Roesky, P. W. 1
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)

Abstract (englisch):
The synthesis of a 1,2,3,4-tetramethylcyclopentadienyl (Cp$^{4}$) substituted four-membered N-heterocyclic silylene [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] is reported first. Then, selected reactions with transition metal and a calcium precursor are shown. The proton of the Cp$_{4}$-unit is labile. This results in two different reaction pathways: (1) deprotonation and (2) rearrangement reactions. Deprotonation was achieved by the reaction of [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] with suitable zinc precursors. Rearrangement to [{PhC(NtBu) $_{2}$}(C$_{5}$Me$_{4}$)SiH], featuring a formally tetravalent silicon R$_{2}$CSi(R′)-H unit, was observed when the proton of the Cp$^{4}$ ring was shifted from the Cp$^{4}$-ring to the silylene in the presence of a Lewis acid. This allows for the coordination of the Cp$^{4}$-ring to a calcium compound. Furthermore, upon reaction with transition metal dimers [MCl(cod)] $_{2}$ (M = Rh, Ir; cod = 1,5-cyclooctadiene) the proton stays at the Cp$^{4}$-ring and the silylene reacts as a sigma donor, which breaks the dimeric structure of the precursors.


Verlagsausgabe §
DOI: 10.5445/IR/1000128204
Veröffentlicht am 25.01.2021
Originalveröffentlichung
DOI: 10.1039/d0sc04174b
Scopus
Zitationen: 6
Web of Science
Zitationen: 4
Dimensions
Zitationen: 6
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 14.12.2020
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000128204
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 11
Heft 46
Seiten 12446-12452
Nachgewiesen in Scopus
Dimensions
Web of Science
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