Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I)
Half-sandwich iron(II) dihalido complexes of the type [Fe(η<sup>5</sup>-Cp’)X<sub>2</sub>]<sup>−</sup> (Cp’ = C<sub>5</sub>H<sub>5</sub> or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, b...
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| Format: | Article |
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MDPI AG
2023-11-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/11/11/437 |
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| author | Julian Zinke Clemens Bruhn Ulrich Siemeling |
| author_facet | Julian Zinke Clemens Bruhn Ulrich Siemeling |
| author_sort | Julian Zinke |
| collection | DOAJ |
| description | Half-sandwich iron(II) dihalido complexes of the type [Fe(η<sup>5</sup>-Cp’)X<sub>2</sub>]<sup>−</sup> (Cp’ = C<sub>5</sub>H<sub>5</sub> or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C<sub>5</sub>H<sub>2</sub>-1,2,4-<i>t</i>Bu<sub>3</sub> ligand. We extended this to homologues [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl, Br, I) containing the particularly popular C<sub>5</sub>Me<sub>5</sub> (Cp*) ligand. Corresponding ionic compounds ER<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] are easily accessible from FeX<sub>2</sub>, MCp* (M = Li, K) and a suitable halide source R<sub>4</sub>EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] (X = Cl, Br), N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)BrCl], and PPh<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)Cl<sub>2</sub>] reacts readily with CO to afford [Fe(η<sup>5</sup>-Cp*)Cl(CO)<sub>2</sub>], indicating the synthetic potential of ER<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] in FeCp* half-sandwich chemistry. |
| first_indexed | 2024-03-09T16:43:57Z |
| format | Article |
| id | doaj.art-5df665be9d7d40acbefeed081e4e636d |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-09T16:43:57Z |
| publishDate | 2023-11-01 |
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| spelling | doaj.art-5df665be9d7d40acbefeed081e4e636d2023-11-24T14:48:28ZengMDPI AGInorganics2304-67402023-11-01111143710.3390/inorganics11110437Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I)Julian Zinke0Clemens Bruhn1Ulrich Siemeling2Institute of Chemistry, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Chemistry, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Chemistry, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyHalf-sandwich iron(II) dihalido complexes of the type [Fe(η<sup>5</sup>-Cp’)X<sub>2</sub>]<sup>−</sup> (Cp’ = C<sub>5</sub>H<sub>5</sub> or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C<sub>5</sub>H<sub>2</sub>-1,2,4-<i>t</i>Bu<sub>3</sub> ligand. We extended this to homologues [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl, Br, I) containing the particularly popular C<sub>5</sub>Me<sub>5</sub> (Cp*) ligand. Corresponding ionic compounds ER<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] are easily accessible from FeX<sub>2</sub>, MCp* (M = Li, K) and a suitable halide source R<sub>4</sub>EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] (X = Cl, Br), N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)BrCl], and PPh<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. N<i>n</i>Pr<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)Cl<sub>2</sub>] reacts readily with CO to afford [Fe(η<sup>5</sup>-Cp*)Cl(CO)<sub>2</sub>], indicating the synthetic potential of ER<sub>4</sub>[Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>] in FeCp* half-sandwich chemistry.https://www.mdpi.com/2304-6740/11/11/437crystal structurescyclopentadienyl complexeshalf-sandwich complexeshalidesiron |
| spellingShingle | Julian Zinke Clemens Bruhn Ulrich Siemeling Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) Inorganics crystal structures cyclopentadienyl complexes half-sandwich complexes halides iron |
| title | Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) |
| title_full | Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) |
| title_fullStr | Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) |
| title_full_unstemmed | Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) |
| title_short | Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η<sup>5</sup>-Cp*)X<sub>2</sub>]<sup>−</sup> (X = Cl − I) |
| title_sort | ammonium and phosphonium salts containing monoanionic iron ii half sandwich complexes fe η sup 5 sup cp x sub 2 sub sup sup x cl i |
| topic | crystal structures cyclopentadienyl complexes half-sandwich complexes halides iron |
| url | https://www.mdpi.com/2304-6740/11/11/437 |
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