A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes
The synthesis of the triarylphosphine, P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> containing a SF<sub>5</sub> group, has been achieved. The experimental and theoretical studies showed that P(<i>p</...
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MDPI AG
2020-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/17/3977 |
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| author | Maria Talavera Silke Hinze Thomas Braun Reik Laubenstein Roy Herrmann |
| author_facet | Maria Talavera Silke Hinze Thomas Braun Reik Laubenstein Roy Herrmann |
| author_sort | Maria Talavera |
| collection | DOAJ |
| description | The synthesis of the triarylphosphine, P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> containing a SF<sub>5</sub> group, has been achieved. The experimental and theoretical studies showed that P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> is a weaker σ-donor when compared with other substituted triarylphosphines, which is consistent with the electron-withdrawing effect of the SF<sub>5</sub> moiety. The studies also revealed a moderate air stability of the phosphine. The σ-donor capabilities of P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> were estimated from the phosphorus-selenium coupling constant in SeP(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> and by DFT calculations. The behavior of P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> as ligand has been investigated by the synthesis of the iridium and rhodium complexes [MCl(COD){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}], [MCl(CO)<sub>2</sub>{P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}<sub>2</sub>] (M = Ir, Rh), or [Rh(<i>µ</i>-Cl)(COE){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}]<sub>2</sub>, and the molecular structures of [IrCl(COD){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}] and [Rh(<i>µ</i>-Cl)(COE){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}]<sub>2</sub> were determined by single X-ray diffraction. The structures revealed a slightly larger cone angle for P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> when compared to other <i>para</i>-substituted triarylphosphines. |
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| spelling | doaj.art-de504841952e4d4d81e9c5ecbe13902c2023-11-20T12:06:17ZengMDPI AGMolecules1420-30492020-09-012517397710.3390/molecules25173977A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir ComplexesMaria Talavera0Silke Hinze1Thomas Braun2Reik Laubenstein3Roy Herrmann4Department of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyDepartment of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyDepartment of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyDepartment of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyDepartment of Chemistry, Humboldt–Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, GermanyThe synthesis of the triarylphosphine, P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> containing a SF<sub>5</sub> group, has been achieved. The experimental and theoretical studies showed that P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> is a weaker σ-donor when compared with other substituted triarylphosphines, which is consistent with the electron-withdrawing effect of the SF<sub>5</sub> moiety. The studies also revealed a moderate air stability of the phosphine. The σ-donor capabilities of P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> were estimated from the phosphorus-selenium coupling constant in SeP(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> and by DFT calculations. The behavior of P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> as ligand has been investigated by the synthesis of the iridium and rhodium complexes [MCl(COD){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}], [MCl(CO)<sub>2</sub>{P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}<sub>2</sub>] (M = Ir, Rh), or [Rh(<i>µ</i>-Cl)(COE){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}]<sub>2</sub>, and the molecular structures of [IrCl(COD){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}] and [Rh(<i>µ</i>-Cl)(COE){P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub>}]<sub>2</sub> were determined by single X-ray diffraction. The structures revealed a slightly larger cone angle for P(<i>p</i>-C<sub>6</sub>H<sub>4</sub>SF<sub>5</sub>)<sub>3</sub> when compared to other <i>para</i>-substituted triarylphosphines.https://www.mdpi.com/1420-3049/25/17/3977fluorosulfanyl groupfluorinated ligandsphosphinesrhodiumiridium |
| spellingShingle | Maria Talavera Silke Hinze Thomas Braun Reik Laubenstein Roy Herrmann A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes Molecules fluorosulfanyl group fluorinated ligands phosphines rhodium iridium |
| title | A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes |
| title_full | A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes |
| title_fullStr | A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes |
| title_full_unstemmed | A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes |
| title_short | A SF<sub>5</sub> Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes |
| title_sort | sf sub 5 sub derivative of triphenylphosphine as an electron poor ligand precursor for rh and ir complexes |
| topic | fluorosulfanyl group fluorinated ligands phosphines rhodium iridium |
| url | https://www.mdpi.com/1420-3049/25/17/3977 |
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