A simple synthesis of group 2 anthracenides and their use as reducing agents for polypnictogen ligand complexes

By using an improved synthetic pathway, the anthracenides of the group 2 metals Ca, Sr, and Ba are straightforwardly accessible for subsequent organometallic syntheses. These highly reactive compounds are slightly soluble in tetrahydrofuran and can be used as synthons for group 2 metal transfer due to the lability of the anthracene substituent. These features were used to explore their reactivity towards the polyphosphorus ligand complexes [Cp*Fe(η<sup>5</sup>-P<sub>5</sub>)] (Cp* = C<sub>5</sub>(CH<sub>3</sub>)<sub>5</sub>) and [Cp*Fe(η<sup>3:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))], respectively. The resulting products, [Cp*Fe(μ-η<sup>4:2:1</sup>-P<sub>5</sub>)Mg(thf)<sub>3</sub>] 0.5 thf (thf = tetrahydrofuran) and [{Cp*Fe(μ-η<sup>2:2:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))}<sub>2</sub>Mg(thf)<sub>2</sub>]·3 thf, are first examples of molecular magnesium-containing polypnictogenide transition metal complexes without stabilization by N-donor ligands that are soluble in organic N-donor-free solvents. The P<sub>12</sub> ligand in the latter complex is the first example of a 2,2'-diphosphanyl-substituted decaphosphadihydrofulvalen-shaped structural motif (2,2'-bis(diphenylphosphanyl)-1,1'-dimethyl-3,3'-bipentaphosphole). The complexes [Cp*Fe(μ<sub>3</sub>-η<sup>4:4:1</sup>-P<sub>5</sub>)Sr(thf)<sub>4</sub>]<sub>2</sub>·2 thf and [Cp*Fe(μ<sub>3</sub>-η<sup>2:1:1:1:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))Sr(thf)<sub>3</sub>]<sub>2</sub>·2 thf represent the first examples of molecular polypnictogen compounds of strontium that are stable in organic solvents.

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Publication Details

Journal
Chemical Science
Published
2025-01-01
DOI
https://doi.org/10.1039/d5sc04242a
Citations
5
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
4.68

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article

A simple synthesis of group 2 anthracenides and their use as reducing agents for polypnictogen ligand complexes

Manfred Scheer, Michael Seidl, Christoph Riesinger, Matthias Weber et al.
5 citations
Chemical Science
Organometallic Complex Synthesis and Catalysis
4.68
article

A simple synthesis of group 2 anthracenides and their use as reducing agents for polypnictogen ligand complexes

Manfred Scheer, Michael Seidl, Christoph Riesinger, Matthias Weber, Lukas Adlbert
article en
5 citations

Abstract

By using an improved synthetic pathway, the anthracenides of the group 2 metals Ca, Sr, and Ba are straightforwardly accessible for subsequent organometallic syntheses. These highly reactive compounds are slightly soluble in tetrahydrofuran and can be used as synthons for group 2 metal transfer due to the lability of the anthracene substituent. These features were used to explore their reactivity towards the polyphosphorus ligand complexes [Cp*Fe(η<sup>5</sup>-P<sub>5</sub>)] (Cp* = C<sub>5</sub>(CH<sub>3</sub>)<sub>5</sub>) and [Cp*Fe(η<sup>3:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))], respectively. The resulting products, [Cp*Fe(μ-η<sup>4:2:1</sup>-P<sub>5</sub>)Mg(thf)<sub>3</sub>] 0.5 thf (thf = tetrahydrofuran) and [{Cp*Fe(μ-η<sup>2:2:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))}<sub>2</sub>Mg(thf)<sub>2</sub>]·3 thf, are first examples of molecular magnesium-containing polypnictogenide transition metal complexes without stabilization by N-donor ligands that are soluble in organic N-donor-free solvents. The P<sub>12</sub> ligand in the latter complex is the first example of a 2,2'-diphosphanyl-substituted decaphosphadihydrofulvalen-shaped structural motif (2,2'-bis(diphenylphosphanyl)-1,1'-dimethyl-3,3'-bipentaphosphole). The complexes [Cp*Fe(μ<sub>3</sub>-η<sup>4:4:1</sup>-P<sub>5</sub>)Sr(thf)<sub>4</sub>]<sub>2</sub>·2 thf and [Cp*Fe(μ<sub>3</sub>-η<sup>2:1:1:1:1</sup>-(1-CH<sub>3</sub>-2-PPh<sub>2</sub>-P<sub>5</sub>))Sr(thf)<sub>3</sub>]<sub>2</sub>·2 thf represent the first examples of molecular polypnictogen compounds of strontium that are stable in organic solvents.

Chemical ScienceVol. 16(34)
Universität Innsbruck (AT), University of Regensburg (DE)
Deutsche Forschungsgemeinschaft, Studienstiftung des Deutschen Volkes
Openalex Percentile: Top 5%
Organometallic Complex Synthesis and Catalysis
4.68
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A simple synthesis of group 2 anthracenides and their use as reducing agents for polypnictogen ligand complexes — Manfred Scheer, Michael Seidl, et al. · Chemical Science (2025) | TGRS Research Map | TGRS