Exploring the Limits of Transition-Metal Fluorination at High Pressures

Angewandte Chemie
Jianyan LinGuochun Yang

Abstract

Fluorination is a proven method for challenging the limits of chemistry, both structurally and electronically. Here we explore computationally how pressures below 300 GPa affect the fluorination of several transition metals. A plethora of new structural phases are predicted along with the possibility for synthesizing four unobserved compounds: TcF7 , CdF3 , OsF8 , and IrF8 . The Ir and Os octaflourides are both predicted to be stable as quasi-molecular phases with an unusual cubic ligand coordination, and both compounds formally correspond to a high oxidation state of +8. Electronic-structure analysis reveals that otherwise unoccupied 6p levels are brought down in energy by the combined effects of pressure and a strong ligand field. The valence expansion of Os and Ir enables ligand-to-metal F 2p→M 6p charge transfer that strengthens M-F bonds and decreases the overall bond polarity. The lower stability of IrF8 , and the instability of PtF8 and several other compounds below 300 GPa, is explained by the occupation of M-F antibonding orbitals in octafluorides with a metal-valence-electron count exceeding 8.

References

Mar 4, 2006·Science·Jonathan C CrowhurstA J Nelson
Apr 26, 2006·Inorganic Chemistry·Thomas DrewsKonrad Seppelt
Apr 28, 2006·Angewandte Chemie·Sebastian Riedel, Martin Kaupp
Dec 19, 2006·Inorganic Chemistry·Sebastian Riedel, Martin Kaupp
Mar 4, 1994·Science·T VogtJ K Cockcroft
Apr 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthias Johann Molski, Konrad Seppelt
Oct 7, 2009·Proceedings of the National Academy of Sciences of the United States of America·Eva ZurekAndriy O Lyakhov
Apr 12, 2013·Chemical Communications : Chem Comm·Karl O Christe
Sep 24, 2013·Nature Chemistry·Mao-sheng Miao
Sep 11, 2014·Nature Communications·Jorge Botana, Mao-Sheng Miao
Nov 25, 2014·Chemical Reviews·Konrad Seppelt
Mar 11, 2015·Angewandte Chemie·Pavel Karen
May 20, 2015·Chemistry : a European Journal·Pekka Pyykkö, Wen-Hua Xu
Jul 3, 2015·Angewandte Chemie·Jorge BotanaMao-sheng Miao
Aug 6, 2015·Journal of the American Chemical Society·Guanjun XiaoBo Zou
Nov 14, 2015·Physical Review Letters·Z J XiangX H Chen
Mar 5, 2016·Journal of the American Chemical Society·Guochun YangYanming Ma
Jun 9, 2016·Angewandte Chemie·Haoyu S Yu, Donald G Truhlar
Aug 25, 2016·Chemistry : a European Journal·Martin RahmN W Ashcroft
Jun 4, 2017·Journal of the American Chemical Society·Chanan D SesslerStephen J Lippard
Jun 24, 2017·Angewandte Chemie·Maarten G GoestenEmiel J M Hensen
Nov 16, 2017·Inorganic Chemistry·Adam GrzelakWojciech Grochala
Dec 2, 2017·Angewandte Chemie·Zachary M GeballeRussell J Hemley
Jan 10, 2018·Angewandte Chemie·Shu-Xian HuJun Li
Jul 13, 2018·Journal of the American Chemical Society·Jianyan LinYanming Ma
Oct 3, 2018·Nature Materials·Aron WalshC Richard A Catlow
Dec 1, 2018·Journal of the American Chemical Society·Martin RahmRoald Hoffmann
Mar 14, 2019·Journal of the American Chemical Society·Jianyan LinYanming Ma
Sep 12, 2019·Proceedings of the National Academy of Sciences of the United States of America·Rajkrishna DuttaThomas S Duffy

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Citations

Feb 10, 2021·The Journal of Chemical Physics·Xin DuGuochun Yang
Jan 26, 2021·Frontiers in Chemistry·Changsu CaoJun Li
Jun 25, 2021·Chemical Science·Martin RahmRoberto Cammi
Sep 23, 2021·Physical Chemistry Chemical Physics : PCCP·Shoutao ZhangHanyu Liu

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