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

DOI: 10.1107/S2052520614008786 DOI Help
PMID: 24892594 PMID Help

Authors: Dave Allan (Diamond Light Source) , Daniel Bailey (The University of Nottingham) , Nigel Bird (The University of Nottingham) , Alexander J. Blake (The University of Nottingham) , Neil R. Champness (The University of Nottingham) , Deguang Huang (The University of Nottingham) , Conal P. Keane (The University of Nottingham) , Jonathan Mcmaster (The University of Nottingham) , Tim Prior (University of Hull) , Jeremiah Tidey (The University of Nottingham) , Martin Schröder (The University of Nottingham)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acta Crystallographica Section B Structural Science, Crystal Engineering And Materials , VOL 70 , PAGES 469 - 486

State: Published (Approved)
Published: June 2014
Diamond Proposal Number(s): 1022 , 1216 , 3031 , 6409 , 7532

Abstract: The mononuclear macrocyclic Pd-II complex cis[PdCl2([9]aneS(3))]([9]aneS(3) = 1,4,7-trithiacyclo-nonane) converts at 44 kbar 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 [PtCl2([9]aneS(3))], [PdBr2([9]aneS(3))], [PtBr2([9]aneS(3))], [PdI2([9]aneS(3))] and [PtI2([9]aneS(3))] 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]aneS(3))] undergoes a phase change. Pressure-induced I center dot center dot center dot I interactions were observed for [PdI2([9]aneS(3))] and [PtI2([9]aneS(3))] at 19 kbar, but the corresponding Br center dot center dot center dot Br interactions in [PdBr2([9]aneS(3))] and [PtBr2([9]aneS(3))] only become significant at much higher pressure (58 kbar). Accompanying density functional theory (DFT) calculations have yielded interaction energies and bond orders for the sulfur-metal interactions.

Journal Keywords: High Pressure; Coordination Complexes; Macrocycle; Intermolecular Contacts; Conformation; Polymerization

Subject Areas: Chemistry, Materials

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 17/09/2014 11:10

Discipline Tags:

Molecular Complexes Chemistry Materials Science Polymer Science

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)