Jason is currently enjoying being a guest Professor at the University of Osaka, Japan. He is being hosted by Prof. Konno and his staff Dr’s Yoshinari, Kuramura, and Kojima. He recently took part in the 2nd International Symposium on Coordination Ionic Compounds along with others from Taiwan, Singapore, Korea, Japan, and the UK (Malcolm Halcrow and Michaela Hardie from the University of Leeds).
Geoff Cloke at 65: a pioneer in organometallic chemistry
Professor Geoff Cloke FRS celebrates his 65th birthday in 2018. In a career spanning four decades, his research endeavours have accounted for some of the most innovative synthetic chemistry of the modern era, with his many publications describing truly exceptional compounds and experimental methods that portray a unique chemical imagination. In addition to his scientific accomplishments, Cloke can be particularly proud of his successful mentoring, a level of dedication that propelled many students and post-docs on to become research leaders in their own right. In compiling this collection of some of his research articles, a small cross-section of his friends, colleagues and collaborators, wish to pay tribute to his modesty, compassion and generous personality.
Radical Relatives: Facile Oxidation of Hetero-Diarylmethene Anions to Neutral Radicals
Inorg. Chem., 2018
Massimiliano Curcio, Daniel Henschel, Mareike Hüttenschmidt, Stephen Sproules, Jason B. Love
ABSTRACT. Furan and thiophene diarylmethenes are potential redox-active ligands for metal centers that could be exploited in the development of non-traditional, stoichiometric, and catalytic redox reactions. As such, we describe here the selective meso-deprotonations of the dithiophene, difuran, and diimine-difuran diarylmethanes to form the p-conjugated anions, for which only the diimino-difuryl anion is truly isolable and studied by X-ray crystallography. In all cases, facile one-electron oxidation of these anions occurs which allows the isolation of the neutral dithienyl and diimino-difuryl radicals. UV-visible and TD-DFT studies reveal that the oxidation of the dithienyl anion to its radical is associated with an increase in the H(S)OMO-LUMO gap, evident through a hypsochromic shift of the main absorption band in the electronic spectrum, whereas oxidation of the diimino-difuryl anion causes only minor spectroscopic changes. Electrochemical studies support the stability of the radicals with respect to the anion, showing strongly negative oxidation potentials. The control of the redox activity of these diarylmethene carbanions through variation of the nature of the substituents, donor-atom, and the conjugated p-system and their potential as ligands for redox-inert metal centers makes them intriguing candidates as non-innocent partners for redox reactions.
Understanding the recovery of rare-earth elements by ammonium salts
Jamie P. Hunter , Sara Dolezalova , Bryne T. Ngwenya , Carole A. Morrison and Jason B. Love
Abstract: While the recovery of rare earth elements (REEs) from aqueous solution by ionic liquids (ILs) has been well documented, the metal compounds that are formed in the organic phase remain poorly characterized. Using spectroscopic, analytical and computational techniques, we provide detailed chemical analysis of the compounds formed in the organic phase during the solvent extraction of REEs by [(n-octyl)3NMe][NO3] (IL). These experiments show that REE recovery using IL is a rapid process and that IL is highly durable. Karl-Fischer measurements signify that the mode of action is unlikely to be micellar, while ions of the general formula REE(NO3)4(IL)2− are detected seen by negative ion mass-spectrometry. Additionally, variable temperature 139La NMR spectroscopy suggests the presence of multiple, low symmetry nitrato species. Classical molecular dynamics simulations show aggregation of multiple ILs around a microhydrated La3+ cation with four nitrates completing the inner coordination sphere. This increased understanding is now being exploited to develop stronger, more selective functionalized ILs for REE recovery.
A CASE PhD studentship (EU/UK) to work with Jason Love and Carole Morrison in collaboration with Johnson Matthey is available.
Please email Jason Love (email@example.com) or Carole Morrison (firstname.lastname@example.org) for further details.