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Issue 46, 2020

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

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Abstract

The synthesis of a 1,2,3,4-tetramethylcyclopentadienyl (Cp4) substituted four-membered N-heterocyclic silylene [{PhC(NtBu)2}Si(C5Me4H)] is reported first. Then, selected reactions with transition metal and a calcium precursor are shown. The proton of the Cp4-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(C5Me4H)] with suitable zinc precursors. Rearrangement to [{PhC(NtBu)2}(C5Me4)SiH], featuring a formally tetravalent silicon R2C[double bond, length as m-dash]Si(R′)–H unit, was observed when the proton of the Cp4 ring was shifted from the Cp4-ring to the silylene in the presence of a Lewis acid. This allows for the coordination of the Cp4-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 Cp4-ring and the silylene reacts as a sigma donor, which breaks the dimeric structure of the precursors.

Graphical abstract: A cyclopentadienyl functionalized silylene – a flexible ligand for Si- and C-coordination

Supplementary files

Article information


Submitted
30 Jul 2020
Accepted
13 Oct 2020
First published
26 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 12446-12452
Article type
Edge Article

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

S. Kaufmann, F. Krätschmer, R. Köppe, T. Schon, C. Schoo and P. W. Roesky, Chem. Sci., 2020, 11, 12446 DOI: 10.1039/D0SC04174B

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