Stimulus-responsive metallocenes: a photo/thermal switch enabled by the perfluorinated Cp* ligand

The electron-deficient ferrocene [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>)] is complemented by the synthesis and full characterisation of the analogous bench-stable ruthenocene [Ru(C<sub>5</sub>H<sub>5</sub>)(C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>)]. These complexes have been studied with respect to the substitution lability of the perfluorinated Cp* ligand under mild conditions. Photolysis of the metallocenes in MeCN converted the [C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]<sup>-</sup> ligand into a weakly coordinating anion. This gave access to the highly reactive piano-stool complexes [M(C<sub>5</sub>H<sub>5</sub>)(MeCN)<sub>3</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>] (M = Fe, Ru). The unstable iron half-sandwich complex dismutates under formation of [Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>] and [Fe(MeCN)<sub>6</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]<sub>2</sub>. It was trapped by the chelating diphosphine DPPE and isolated as thermally stable [Fe(C<sub>5</sub>H<sub>5</sub>)(DPPE)(MeCN)][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]. For [Ru(C<sub>5</sub>H<sub>5</sub>)(MeCN)<sub>3</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>] a thermally induced backreaction to ruthenocene is observed. This represents the first example of a reversible dissociation and recoordination of a cyclopentadienyl ligand, initiated by light and heat.

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Publication Details

Journal
Chemical Science
Published
2025-01-01
DOI
https://doi.org/10.1039/d5sc02784e
Citations
1
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
0.94

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article

Stimulus-responsive metallocenes: a photo/thermal switch enabled by the perfluorinated Cp* ligand

Tim‐Niclas Streit, Paulin S. Riemann, Nils Hartmann, Moritz Malischewski et al.
1 citations
Chemical Science
Organometallic Complex Synthesis and Catalysis
0.94
article

Stimulus-responsive metallocenes: a photo/thermal switch enabled by the perfluorinated Cp* ligand

Tim‐Niclas Streit, Paulin S. Riemann, Nils Hartmann, Moritz Malischewski, Robin Sievers
article en
1 citations

Abstract

The electron-deficient ferrocene [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>)] is complemented by the synthesis and full characterisation of the analogous bench-stable ruthenocene [Ru(C<sub>5</sub>H<sub>5</sub>)(C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>)]. These complexes have been studied with respect to the substitution lability of the perfluorinated Cp* ligand under mild conditions. Photolysis of the metallocenes in MeCN converted the [C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]<sup>-</sup> ligand into a weakly coordinating anion. This gave access to the highly reactive piano-stool complexes [M(C<sub>5</sub>H<sub>5</sub>)(MeCN)<sub>3</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>] (M = Fe, Ru). The unstable iron half-sandwich complex dismutates under formation of [Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>] and [Fe(MeCN)<sub>6</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]<sub>2</sub>. It was trapped by the chelating diphosphine DPPE and isolated as thermally stable [Fe(C<sub>5</sub>H<sub>5</sub>)(DPPE)(MeCN)][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>]. For [Ru(C<sub>5</sub>H<sub>5</sub>)(MeCN)<sub>3</sub>][C<sub>5</sub>(CF<sub>3</sub>)<sub>5</sub>] a thermally induced backreaction to ruthenocene is observed. This represents the first example of a reversible dissociation and recoordination of a cyclopentadienyl ligand, initiated by light and heat.

Chemical ScienceVol. 16(26)
Freie Universität Berlin (DE)
Fonds der Chemischen Industrie, Deutsche Forschungsgemeinschaft, Freie Universität Berlin
Openalex Percentile: Top 26%
Organometallic Complex Synthesis and Catalysis
0.94
DOIOpen Access PDFOpenAlex
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