Unravelling the Structure of Magnus' Pink Salt

Lucier, Bryan E.G.; Johnston, Karen E.; Xu, Wenqian; Hanson, Jonathan C.; Senanayake, Sanjaya D.; Yao, Siyu; Bourassa, Megan W.; Srebro, Monika; Autschbach, Jochen; Schurko, Robert W.

Abstract

A combination of multinuclear ultra-wideline solid-state NMR, powder X-ray diffraction (pXRD), X-ray absorption fine structure experiments, and first principles calculations of platinum magnetic shielding tensors has been employed to reveal the previously unknown crystal structure of Magnus’ pink salt (MPS), [Pt(NH3)4][PtCl4], study the isomeric Magnus’ green salt (MGS), [Pt(NH3)4][PtCl4], and examine their synthetic precursors K2PtCl4 and Pt(NH3)4Cl2·H2O. A simple synthesis of MPS is detailed which produces relatively pure product in good yield. Broad 195Pt, 14N, and 35Cl SSNMR powder patterns have been acquired using the WURST-CPMG and BRAIN-CP/WURST-CPMG pulse sequences. Experimentally measured and theoretically calculated platinum magnetic shielding tensors are shown to be very sensitive to the types and arrangements of coordinating ligands as well as intermolecular Pt–Pt metallophilic interactions. High-resolution 195Pt NMR spectra of select regions of the broad 195Pt powder patterns, in conjunction with an array of 14N and 35Cl spectra, reveal clear structural differences between all compounds. Rietveld refinements of synchrotron pXRD patterns, guided by first principles geometry optimization calculations, yield the space group, unit cell parameters, and atomic positions of MPS. The crystal structure has P-1 symmetry and resides in a pseudotetragonal unit cell with a distance of >5.5 Å between Pt sites in the square-planar Pt units. The long Pt–Pt distances and nonparallel orientation of Pt square planes prohibit metallophilic interactions within MPS. The combination of ultra-wideline NMR, pXRD, and computational methods offers much promise for future investigation and characterization of Pt-containing systems.

Citation

Lucier, B. E., Johnston, K. E., Xu, W., Hanson, J. C., Senanayake, S. D., Yao, S., …Schurko, R. W. (2013). Unravelling the Structure of Magnus' Pink Salt. Journal of the American Chemical Society, 136(4), 1333-1351. https://doi.org/10.1021/ja4076277

• Journal Article Type: Article
• Acceptance Date: Jul 24, 2013
• Online Publication Date: Jan 17, 2014
• Publication Date: Dec 13, 2013
• Deposit Date: Sep 30, 2016
• Publicly Available Date: Aug 28, 2018
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 136
• Issue: 4
• Pages: 1333-1351
• DOI: https://doi.org/10.1021/ja4076277
• Public URL: https://durham-repository.worktribe.com/output/1373477