Issue 20, 2023

Persilylation of ferrocene: the ultimate discipline in sterically overcrowded metal complexes

Abstract

We report the preparation and structural characterization of the first persilylated metallocene via the metalation of decabromoferrocene. Although Grignard conditions turned out to be insufficient due to the steric and electronic effects of silyl groups causing a decreased nucleophilicity of the metalated intermediates, stepwise lithium–halogen exchange yields complex mixtures of polysilylated compounds FeC10DMSnH10−n (n = 10, 9, 8) including the targeted decasilylated ferrocene. These mixtures were successfully separated allowing a systematic study of silylation effects on ferrocene by XRD, CV, NMR and UV/vis spectroscopy supported by DFT calculations. The findings were used to develop a high-yielding and simple preparation method to generate a tenfold substituted overcrowded ferrocene, FeC10DMS8Me2.

Graphical abstract: Persilylation of ferrocene: the ultimate discipline in sterically overcrowded metal complexes

Supplementary files

Article information

Article type
Paper
Submitted
14 Apr 2023
Accepted
19 Apr 2023
First published
19 Apr 2023
This article is Open Access
Creative Commons BY license

Dalton Trans., 2023,52, 6870-6875

Persilylation of ferrocene: the ultimate discipline in sterically overcrowded metal complexes

S. M. Rupf, R. Sievers, P. S. Riemann, M. Reimann, M. Kaupp, C. Fasting and M. Malischewski, Dalton Trans., 2023, 52, 6870 DOI: 10.1039/D3DT01133J

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