Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds
Separate reactions of [Th{N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>2</sub>(CH<sub>2</sub>CH<sub>2</sub>NSi(Me)(Bu<sup>t</sup>)(μ-CH<sub>2</sub>)]<sub>2</sub&...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-04-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/9/5/30 |
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| author | Joseph P. A. Ostrowski Ashley J. Wooles Stephen T. Liddle |
| author_facet | Joseph P. A. Ostrowski Ashley J. Wooles Stephen T. Liddle |
| author_sort | Joseph P. A. Ostrowski |
| collection | DOAJ |
| description | Separate reactions of [Th{N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>2</sub>(CH<sub>2</sub>CH<sub>2</sub>NSi(Me)(Bu<sup>t</sup>)(μ-CH<sub>2</sub>)]<sub>2</sub> (<b>1</b>) with [Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(H)] (<b>2</b>) or [Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(H)(CO)<sub>2</sub>] (<b>3</b>) produced, by alkane elimination, [Th(Tren<sup>DMBS</sup>)Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>] (<b>ThRe</b>, Tren<sup>DMBS</sup> = {N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>3</sub>}<sup>3-</sup>), and [Th(Tren<sup>DMBS</sup>)Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>] (<b>ThRu</b>), which were isolated in crystalline yields of 71% and 62%, respectively. Complex <b>ThRe</b> is the first example of a molecular Th-Re bond to be structurally characterised, and <b>ThRu</b> is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds. |
| first_indexed | 2024-03-10T12:06:43Z |
| format | Article |
| id | doaj.art-68a683d19c6f4b0b98ec187edbfe0463 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-10T12:06:43Z |
| publishDate | 2021-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-68a683d19c6f4b0b98ec187edbfe04632023-11-21T16:33:06ZengMDPI AGInorganics2304-67402021-04-01953010.3390/inorganics9050030Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium BondsJoseph P. A. Ostrowski0Ashley J. Wooles1Stephen T. Liddle2Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UKDepartment of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UKDepartment of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UKSeparate reactions of [Th{N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>2</sub>(CH<sub>2</sub>CH<sub>2</sub>NSi(Me)(Bu<sup>t</sup>)(μ-CH<sub>2</sub>)]<sub>2</sub> (<b>1</b>) with [Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(H)] (<b>2</b>) or [Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(H)(CO)<sub>2</sub>] (<b>3</b>) produced, by alkane elimination, [Th(Tren<sup>DMBS</sup>)Re(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>] (<b>ThRe</b>, Tren<sup>DMBS</sup> = {N(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>2</sub>Bu<sup>t</sup>)<sub>3</sub>}<sup>3-</sup>), and [Th(Tren<sup>DMBS</sup>)Ru(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>] (<b>ThRu</b>), which were isolated in crystalline yields of 71% and 62%, respectively. Complex <b>ThRe</b> is the first example of a molecular Th-Re bond to be structurally characterised, and <b>ThRu</b> is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds.https://www.mdpi.com/2304-6740/9/5/30thoriumrheniumrutheniummetal–metal bondsuraniumdensity functional theory |
| spellingShingle | Joseph P. A. Ostrowski Ashley J. Wooles Stephen T. Liddle Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds Inorganics thorium rhenium ruthenium metal–metal bonds uranium density functional theory |
| title | Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds |
| title_full | Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds |
| title_fullStr | Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds |
| title_full_unstemmed | Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds |
| title_short | Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds |
| title_sort | synthesis and characterisation of molecular polarised covalent thorium rhenium and ruthenium bonds |
| topic | thorium rhenium ruthenium metal–metal bonds uranium density functional theory |
| url | https://www.mdpi.com/2304-6740/9/5/30 |
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