High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes

Schr�der, Martin

Abstract

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.

Citation

Schröder, M. (2014). High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, B70, https://doi.org/10.1107/S2052520614008786

• Journal Article Type: Article
• Publication Date: Jan 1, 2014
• Deposit Date: Aug 26, 2015
• Publicly Available Date: Aug 26, 2015
• Journal: Acta Crystallographica Section B
• Print ISSN: 2052-5192
• Electronic ISSN: 2052-5206
• Publisher: International Union of Crystallography
• Peer Reviewed: Peer Reviewed
• Volume: B70
• DOI: https://doi.org/10.1107/S2052520614008786
• Keywords: High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation
• Public URL: https://nottingham-repository.worktribe.com/output/999788
• Publisher URL: http://scripts.iucr.org/cgi-bin/paper?S2052520614008786
• Additional Information: Schröder, M. High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B, B70, pp. 469-486.