A matrix isolation and computational study of molecular palladium fluorides : does PdF₆ exist?

Wilson, Antony V.; Nguyen, Timothy; Brosi, Felix; Wang, Xuefeng; Andrews, Lester; Riedel, Sebastian; Bridgeman, Adam J.; Young, Nigel A.

Abstract

Palladium atoms generated by thermal evaporation and laser ablation were reacted with and trapped in F₂ /Ar, F₂ /Ne, and neat F₂ matrices. The products were characterized by electronic absorption and infrared spectroscopy, together with relativistic density functional theory calculations as well as coupled cluster calculations. Vibrational modes at 540 and 617 cm⁻¹ in argon matrices were assigned to molecular PdF and PdF₂ , and a band at 692 cm⁻¹ was assigned to molecular PdF₄ . A band at 624 cm⁻¹ can be assigned to either PdF₃ or PdF₆, with the former preferred from experimental considerations. Although calculations might support the latter assignment, our conclusion is that in these detailed experiments there is no convincing evidence for PdF₆.

Citation

Wilson, A. V., Nguyen, T., Brosi, F., Wang, X., Andrews, L., Riedel, S., Bridgeman, A. J., & Young, N. A. (2016). A matrix isolation and computational study of molecular palladium fluorides : does PdF₆ exist?. Inorganic chemistry, 55(3), 1108-1123. https://doi.org/10.1021/acs.inorgchem.5b02273

• Journal Article Type: Article
• Acceptance Date: Dec 16, 2015
• Online Publication Date: Jan 8, 2016
• Publication Date: Feb 1, 2016
• Deposit Date: Mar 2, 2016
• Publicly Available Date: Mar 2, 2016
• Journal: Inorganic chemistry
• Print ISSN: 0020-1669
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 55
• Issue: 3
• Pages: 1108-1123
• DOI: https://doi.org/10.1021/acs.inorgchem.5b02273
• Keywords: Matrix isolation, PdF₆, Palladium atoms
• Public URL: https://hull-repository.worktribe.com/output/412018
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b02273
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/acs.inorgchem.5b02273
• Contract Date: Mar 2, 2016