High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes

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

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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.

Item Type: Article
Additional Information: Schröder, M. High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B, B70, pp. 469-486.
Keywords: High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1107/S2052520614008786
Depositing User: Schroder, Martin
Date Deposited: 26 Aug 2015 11:43
Last Modified: 08 Dec 2016 22:31
URI: http://eprints.nottingham.ac.uk/id/eprint/29689

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