Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se)
Diiron μ-aminocarbyne complexes [Fe<sub>2</sub>Cp<sub>2</sub>(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF<sub>3</sub>SO<sub>3</sub> (R = Xyl, <b>[1a<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = Me, <b>[...
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| Format: | Article |
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MDPI AG
2023-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/7/3251 |
| _version_ | 1797607311786639360 |
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| author | Giulio Bresciani Stefano Zacchini Guido Pampaloni Marco Bortoluzzi Fabio Marchetti |
| author_facet | Giulio Bresciani Stefano Zacchini Guido Pampaloni Marco Bortoluzzi Fabio Marchetti |
| author_sort | Giulio Bresciani |
| collection | DOAJ |
| description | Diiron μ-aminocarbyne complexes [Fe<sub>2</sub>Cp<sub>2</sub>(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF<sub>3</sub>SO<sub>3</sub> (R = Xyl, <b>[1a<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = Me, <b>[1b<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = Cy, <b>[1c<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = CH<sub>2</sub>Ph, <b>[1d<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>), freshly prepared from tricarbonyl precursors <b>[1a–d]CF<sub>3</sub>SO<sub>3</sub></b>, reacted with NaOCN (in acetone) and NBu<sub>4</sub>SCN (in dichloromethane) to give [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCO)(CO)(μ-CO){μ-CN(Me)(R)}] (R = Xyl, <b>2a</b>; Me, <b>2b</b>; Cy, <b>2c</b>) and [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCS)(CO)(μ-CO){μ-CN(Me)(CH<sub>2</sub>Ph)}], <b>3</b> in 67–81% yields via substitution of the acetonitrile ligand. The reaction of <b>[1a<sup>NCMe</sup>–1c<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b> with KSeCN in THF at reflux temperature led to the cyanide complexes [Fe<sub>2</sub>Cp<sub>2</sub>(CN)(CO)(μ-CO){μ-CNMe(R)}], <b>6a</b>–<b>c</b> (45–67%). When the reaction of <b>[1a<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b> with KSeCN was performed in acetone at room temperature, subsequent careful chromatography allowed the separation of moderate amounts of [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>Se</i>-SeCN)(CO)(μ-CO){μ-CN(Me)(Xyl)}], <b>4a</b>, and [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCSe)(CO)(μ-CO){μ-CN(Me)(Xyl)}], <b>5a</b>. All products were fully characterized by elemental analysis, IR, and multinuclear NMR spectroscopy; moreover, the molecular structure of <b><i>trans</i>-6b</b> was ascertained by single crystal X-ray diffraction. DFT calculations were carried out to shed light on the coordination mode and stability of the {NC<i>Se</i>-} fragment. |
| first_indexed | 2024-03-11T05:28:22Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T05:28:22Z |
| publishDate | 2023-04-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-0354c87d11434d91bbe11b237ad55a562023-11-17T17:15:45ZengMDPI AGMolecules1420-30492023-04-01287325110.3390/molecules28073251Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se)Giulio Bresciani0Stefano Zacchini1Guido Pampaloni2Marco Bortoluzzi3Fabio Marchetti4Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, I-56124 Pisa, ItalyInteruniversity Consortium for Chemical Reactivity and Catalysis, CIRCC, Via Celso Ulpiani 27, I-70126 Bari, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, I-56124 Pisa, ItalyInteruniversity Consortium for Chemical Reactivity and Catalysis, CIRCC, Via Celso Ulpiani 27, I-70126 Bari, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, I-56124 Pisa, ItalyDiiron μ-aminocarbyne complexes [Fe<sub>2</sub>Cp<sub>2</sub>(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF<sub>3</sub>SO<sub>3</sub> (R = Xyl, <b>[1a<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = Me, <b>[1b<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = Cy, <b>[1c<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>; R = CH<sub>2</sub>Ph, <b>[1d<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b>), freshly prepared from tricarbonyl precursors <b>[1a–d]CF<sub>3</sub>SO<sub>3</sub></b>, reacted with NaOCN (in acetone) and NBu<sub>4</sub>SCN (in dichloromethane) to give [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCO)(CO)(μ-CO){μ-CN(Me)(R)}] (R = Xyl, <b>2a</b>; Me, <b>2b</b>; Cy, <b>2c</b>) and [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCS)(CO)(μ-CO){μ-CN(Me)(CH<sub>2</sub>Ph)}], <b>3</b> in 67–81% yields via substitution of the acetonitrile ligand. The reaction of <b>[1a<sup>NCMe</sup>–1c<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b> with KSeCN in THF at reflux temperature led to the cyanide complexes [Fe<sub>2</sub>Cp<sub>2</sub>(CN)(CO)(μ-CO){μ-CNMe(R)}], <b>6a</b>–<b>c</b> (45–67%). When the reaction of <b>[1a<sup>NCMe</sup>]CF<sub>3</sub>SO<sub>3</sub></b> with KSeCN was performed in acetone at room temperature, subsequent careful chromatography allowed the separation of moderate amounts of [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>Se</i>-SeCN)(CO)(μ-CO){μ-CN(Me)(Xyl)}], <b>4a</b>, and [Fe<sub>2</sub>Cp<sub>2</sub>(k<i>N</i>-NCSe)(CO)(μ-CO){μ-CN(Me)(Xyl)}], <b>5a</b>. All products were fully characterized by elemental analysis, IR, and multinuclear NMR spectroscopy; moreover, the molecular structure of <b><i>trans</i>-6b</b> was ascertained by single crystal X-ray diffraction. DFT calculations were carried out to shed light on the coordination mode and stability of the {NC<i>Se</i>-} fragment.https://www.mdpi.com/1420-3049/28/7/3251organometallic chemistrydiiron complexesaminocarbyne ligandselenocyanatesubstitution reactions |
| spellingShingle | Giulio Bresciani Stefano Zacchini Guido Pampaloni Marco Bortoluzzi Fabio Marchetti Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) Molecules organometallic chemistry diiron complexes aminocarbyne ligand selenocyanate substitution reactions |
| title | Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) |
| title_full | Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) |
| title_fullStr | Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) |
| title_full_unstemmed | Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) |
| title_short | Diiron Aminocarbyne Complexes with NCE<sup>−</sup> Ligands (E = O, S, Se) |
| title_sort | diiron aminocarbyne complexes with nce sup sup ligands e o s se |
| topic | organometallic chemistry diiron complexes aminocarbyne ligand selenocyanate substitution reactions |
| url | https://www.mdpi.com/1420-3049/28/7/3251 |
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