High-pressure studies of palladium and platinum thioether macrocyclic dihalide complexes

Allan, David R.; Bailey, Daniel; Bird, Nigel; Blake, Alexander J.; Champness, Neil R.; Huang, Deguang; Keane, Conal P.; McMaster, Jonathan; Prior, Timothy J.; Tidey, Jeremiah P.; Schröder, Martin

Abstract

The mononuclear macrocyclic PdII complex cis-[PdCl 2([9]aneS3)] ([9]aneS3 = 1,4,7-trithiacyclo- nonane) converts at 44kbar into an intensely coloured chain polymer exhibiting distorted octahedral coordination at the metal centre and an unprecedented [1233] conformation for the thioether ligand. The evolution of an intramolecular axial sulfur-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 [PtCl 2([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 19kbar, but the corresponding Br⋯Br interactions in [PdBr2([9]aneS3)] and [PtBr2([9]aneS3)] only become significant at much higher pressure (58kbar). Accompanying density functional theory (DFT) calculations have yielded interaction energies and bond orders for the sulfur-metal interactions. © 2014 International Union of Crystallography.

Citation

Allan, D. R., Bailey, D., Bird, N., Blake, A. J., Champness, N. R., Huang, D., Keane, C. P., McMaster, J., Prior, T. J., Tidey, J. P., & Schröder, M. (2014). High-pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 70(3), 469-486. https://doi.org/10.1107/S2052520614008786

• Journal Article Type: Article
• Acceptance Date: Apr 17, 2014
• Publication Date: 2014
• Deposit Date: Apr 1, 2022
• Journal: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
• Print ISSN: 2052-5192
• Electronic ISSN: 2052-5206
• Publisher: International Union of Crystallography
• Peer Reviewed: Peer Reviewed
• Volume: 70
• Issue: 3
• Pages: 469-486
• DOI: https://doi.org/10.1107/S2052520614008786
• Keywords: High pressure; Coordination complexes; Macrocycle; Intermolecular contacts; Conformation; Polymerization
• Public URL: https://www.scopus.com/inward/record.uri?eid=2-s2.0-84902116279&doi=10.1107%2fS2052520614008786&partnerID=40&md5=8e3d7651d01463e03b5d9615b78ad9ca