Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine
The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (<b>19</b>) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)<sub>2</sub>(<b>19<...
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MDPI AG
2022-11-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/10/11/203 |
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| author | Peter A. Cleaves Ben Gourlay Margot Marseglia Daniel J. Ward Stephen M. Mansell |
| author_facet | Peter A. Cleaves Ben Gourlay Margot Marseglia Daniel J. Ward Stephen M. Mansell |
| author_sort | Peter A. Cleaves |
| collection | DOAJ |
| description | The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (<b>19</b>) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)<sub>2</sub>(<b>19</b>)] (<b>21</b>) was synthesized in 32% yield and comprehensibly characterized (multinuclear NMR spectroscopy, elemental analysis, mass spectrometry and single-crystal X-ray diffraction). The monogold species showed no <sup>31</sup>P nuclear magnetic resonance at 25 °C but two resonances at −70 °C due to rapid exchange of AuCl between the phosphinine donors at 25 °C and was also susceptible to redistribution reactions to form the digold species. Analogous reactions of [AuCl(tht)] with 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (<b>22</b>) revealed preferential coordination of the AuCl unit to the PPh<sub>2</sub> donor first, with coordination to the phosphinine achieved upon reaction with the second equivalent of [AuCl(tht)]. Unexpectedly, the digold complex was not stable, undergoing decomposition to give an unidentified black precipitate. Structural information could only be obtained on the digold hydrolysis product [(AuCl)<sub>2</sub>(1-OH-2-PPh<sub>2</sub>-3-MePC<sub>5</sub>H<sub>4</sub>)], which showed an aurophilic interaction. |
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| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-09T18:15:39Z |
| publishDate | 2022-11-01 |
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| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-59899acdce9144b696bfe8cb8e93b12b2023-11-24T08:45:46ZengMDPI AGInorganics2304-67402022-11-01101120310.3390/inorganics10110203Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-PhosphinophosphininePeter A. Cleaves0Ben Gourlay1Margot Marseglia2Daniel J. Ward3Stephen M. Mansell4Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKInstitute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UKThe reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (<b>19</b>) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)<sub>2</sub>(<b>19</b>)] (<b>21</b>) was synthesized in 32% yield and comprehensibly characterized (multinuclear NMR spectroscopy, elemental analysis, mass spectrometry and single-crystal X-ray diffraction). The monogold species showed no <sup>31</sup>P nuclear magnetic resonance at 25 °C but two resonances at −70 °C due to rapid exchange of AuCl between the phosphinine donors at 25 °C and was also susceptible to redistribution reactions to form the digold species. Analogous reactions of [AuCl(tht)] with 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (<b>22</b>) revealed preferential coordination of the AuCl unit to the PPh<sub>2</sub> donor first, with coordination to the phosphinine achieved upon reaction with the second equivalent of [AuCl(tht)]. Unexpectedly, the digold complex was not stable, undergoing decomposition to give an unidentified black precipitate. Structural information could only be obtained on the digold hydrolysis product [(AuCl)<sub>2</sub>(1-OH-2-PPh<sub>2</sub>-3-MePC<sub>5</sub>H<sub>4</sub>)], which showed an aurophilic interaction.https://www.mdpi.com/2304-6740/10/11/203phosphininephosphorus ligandsgold complexesligand properties |
| spellingShingle | Peter A. Cleaves Ben Gourlay Margot Marseglia Daniel J. Ward Stephen M. Mansell Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine Inorganics phosphinine phosphorus ligands gold complexes ligand properties |
| title | Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine |
| title_full | Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine |
| title_fullStr | Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine |
| title_full_unstemmed | Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine |
| title_short | Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine |
| title_sort | digold phosphinine complexes are stable with a bis phosphinine ligand but not with a 2 phosphinophosphinine |
| topic | phosphinine phosphorus ligands gold complexes ligand properties |
| url | https://www.mdpi.com/2304-6740/10/11/203 |
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