Issue 46, 2020

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

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

Article type
Edge Article
Submitted
30 Jūl. 2020
Accepted
13 Okt. 2020
First published
26 Okt. 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 12446-12452

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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