High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes
The mononuclear macrocyclic Pd(II) complex cis-[PdCl2([9 aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane) converts at 44 kbar into an intensely coloured chain polymer exhibiting distorted octahedral co-ordination at the metal centre and an unprecedented [1233] conformation for the thioether ligand. The...
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International Union of Crystallography
2014
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| Online Access: | https://eprints.nottingham.ac.uk/29689/ |
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| author | Schröder, Martin |
| author_facet | Schröder, Martin |
| author_sort | Schröder, Martin |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The mononuclear macrocyclic Pd(II) complex cis-[PdCl2([9 aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane) converts at 44 kbar into an intensely coloured chain polymer exhibiting distorted octahedral co-ordination at the metal centre and an unprecedented [1233] conformation for the thioether ligand. The evolution of an intramolecular axial sulphur metal interaction and an intermolecular equatorial sulfur-metal interaction is central to these changes. High pressure crystallographic experiments have also been undertaken on the related complexes [PtCl2([9]aneS3)], [PdBr2([9]aneS3)],[PtBr2([9]aneS3)], [PdI2([9]aneS3)] and [PtI2([9]aneS3)] in order to establish the effects of changing the halide ligands and the metal centre on the behaviour of these complexes under pressure. While all complexes undergo contraction of the various interaction distances with increasing pressure, only[PdCl2([9]aneS3)] undergoes a phase change. Pressure-induced I…I interactions were observed for [PdI2([9]aneS3)] and [PtI2([9]aneS3)] at 19 kbar but the corresponding Br…Br interactions in [PdBr2([9]aneS3)] and [PtBr2([9]aneS3)] only become significant at much higher pressure (58 kbar. Accompanying DFT calculations have yielded interaction energies and bond orders for the sulphur metal interactions. |
| first_indexed | 2025-11-14T19:06:34Z |
| format | Article |
| id | nottingham-29689 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:06:34Z |
| publishDate | 2014 |
| publisher | International Union of Crystallography |
| recordtype | eprints |
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| spelling | nottingham-296892020-05-04T20:17:47Z https://eprints.nottingham.ac.uk/29689/ High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes Schröder, Martin The mononuclear macrocyclic Pd(II) complex cis-[PdCl2([9 aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane) converts at 44 kbar into an intensely coloured chain polymer exhibiting distorted octahedral co-ordination at the metal centre and an unprecedented [1233] conformation for the thioether ligand. The evolution of an intramolecular axial sulphur metal interaction and an intermolecular equatorial sulfur-metal interaction is central to these changes. High pressure crystallographic experiments have also been undertaken on the related complexes [PtCl2([9]aneS3)], [PdBr2([9]aneS3)],[PtBr2([9]aneS3)], [PdI2([9]aneS3)] and [PtI2([9]aneS3)] in order to establish the effects of changing the halide ligands and the metal centre on the behaviour of these complexes under pressure. While all complexes undergo contraction of the various interaction distances with increasing pressure, only[PdCl2([9]aneS3)] undergoes a phase change. Pressure-induced I…I interactions were observed for [PdI2([9]aneS3)] and [PtI2([9]aneS3)] at 19 kbar but the corresponding Br…Br interactions in [PdBr2([9]aneS3)] and [PtBr2([9]aneS3)] only become significant at much higher pressure (58 kbar. Accompanying DFT calculations have yielded interaction energies and bond orders for the sulphur metal interactions. International Union of Crystallography 2014 Article PeerReviewed Schröder, Martin (2014) High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B, B70 . pp. 469-486. ISSN 2052-5206 High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation http://scripts.iucr.org/cgi-bin/paper?S2052520614008786 doi:10.1107/S2052520614008786 doi:10.1107/S2052520614008786 |
| spellingShingle | High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation Schröder, Martin High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title | High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title_full | High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title_fullStr | High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title_full_unstemmed | High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title_short | High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| title_sort | high pressure studies of palladium and platinum thioether macrocyclic dihalide complexes |
| topic | High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation |
| url | https://eprints.nottingham.ac.uk/29689/ https://eprints.nottingham.ac.uk/29689/ https://eprints.nottingham.ac.uk/29689/ |