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High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes

Schröder, Martin

Authors

Martin Schröder M.Schroder@man.ac.uk



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.

Journal Article Type Article
Publication Date Jan 1, 2014
Journal Acta Crystallographica Section B
Print ISSN 2052-5192
Electronic ISSN 2052-5206
Publisher International Union of Crystallography
Peer Reviewed Peer Reviewed
Volume B70
APA6 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, doi:10.1107/S2052520614008786
DOI https://doi.org/10.1107/S2052520614008786
Keywords High pressure; coordination complexes; palladium; platinum; macrocycle; intermolecular contacts; conformation; polymerisation
Publisher URL http://scripts.iucr.org/cgi-bin/paper?S2052520614008786
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information Schröder, M. High pressure studies of palladium and platinum thioether macrocyclic dihalide complexes. Acta Crystallographica Section B, B70, pp. 469-486.

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf


HP Paper Supplementary Information 16-4-2014.pdf (1.6 Mb)
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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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