Big in Japan

Lotte, Jamie, and Liam presenting their work in Nagoya – dehydrated and hot, but happy!

Japan2019

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New publication in Inorganic Chemistry

Proton Chelating Ligands Drive Improved Chemical Separations for Rhodium

Hirokazu Narita*, Rebecca M. Nicolson, Ryuhei Motokawa, Fumiyuki Ito, Kazuko Morisaku, Midori Goto, Mikiya Tanaka, William T. Heller, Hideaki Shiwaku, Tsuyoshi Yaita, Ross J. Gordon, Jason B. Love, Peter A. Tasker, Emma R. Schofield, Mark R. Antonio, Carole A. Morrison*

Inorg. Chem., 2019, 10.1021/acs.inorgchem.9b01136

IC2019Rh

Current methods for the extraction of rhodium carry the highest carbon footprint and worst pollution metrics of all of the elements used in modern technological applications. Improving upon existing methods is made difficult by the limited understanding of the molecular-level chemistry occurring in extraction processes, particularly in the hydrometallurgical separation step. While many of the precious metals can be separated by solvent extraction, there currently exist no commercial extractants for Rh. This is due to its complicated mixed speciation upon leaching into hydrochloric acid, which gives rise to difficulties in designing effective reagents for solvent extraction. Herein we show that the diamidoamine reagent Nn-hexylbis(N-methyl-Nn-octylethylamide)amine transports Rh(III) from aqueous HCl into an organic phase as the monoaquated dianion [RhCl5(H2O)]2– through the formation of an outer-sphere assembly; this assembly has been characterized by experimentation (slope analysis, FT-IR and NMR spectroscopy, EXAFS, SANS, and ESI-MS) and computational modeling. The paper demonstrates the importance of applying a broad range of techniques to obtain a convincing mode of action for the complex processes involved in anion recognition in the solution phase. A consistent and comprehensive understanding of how the ligand operates to achieve Rh(III) selectivity over the competitor anion Cl has emerged. This knowledge will guide the design of extractants and thus offers promise for improving the sustainability of metal extraction from both traditional mining sources and the recycling of secondary source materials.

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New publication in Dalton Transactions

Polynuclear alkoxy-zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

James R. Pankhurst, Shyeni Paul, Yunqing Zhu, Charlotte K. Williams, Jason B. Love

ToC_Dalton_2019

The reactions between alcohols and the tetranuclear ethyl-Zn complexes of an ortho-phenylene-bridged polypyrrole macrocycle, Zn4Et4(L3) 1 and the related anthracenyl-bridged macrocyclic complex, Zn4Et4(THF)4(L4) 2 have been studied. With long-chain alcohols such as n-hexanol, the clean formation of the tetranuclear hexoxide complex Zn4(OC6H13)4(L3) 3 occurs. In contrast, the use of shorter-chain alcohols such as i-propanol results in the trinuclear complex Zn32-OiPr)23-OiPr)(HL3) 4 that arises from demetalation; this complex was characterised by X-ray crystallography. The clean formation of these polynuclear zinc clusters allowed a study of their use as catalysts in the ring-opening copolymerisation (ROCOP) reaction between cyclohexene oxide and CO2. In-situ reactions involving the pre-catalyst 1 and n-hexanol formed the desired polymer with the best selectivity for polycarbonate (90 %) at 30 atm CO2, whilst the activity and performance of pre-catalyst 2 was poor in comparison.

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Welcome Elena

 

Elena HoppenerElena Höppener has joined the group as a research intern for 5 months. She graduated with a bachelors degree in chemistry at Utrecht University in the Netherlands and is currently enrolled in the Masters program Nanomaterials Science at Utrecht University working with Prof. Bert Klein Gebbink. She will be working on the synthesis and characterization of new dipyrrin Pacman complexes and their properties in redox chemistry.

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New publication in ChemCatChem

Controlled Photocatalytic Hydrocarbon Oxidation by Uranyl Complexes

ChemCatChem2019

Polly Arnold, Jamie Purkis, Ryte Rutkauskaite, Daniel Kovacs, Jason Love, Jonathan Austin

Controlled, photocatalytic C−H bond activations are key reactions in the toolkits of the modern synthetic chemist. While it is known that the uranyl(VI) ion, [UVIO2]2+, the environmentally dominant form of uranium, is photoactive, most literature examines its luminescent properties, neglecting its potential synthetic utility for photocatalytic C−H bond cleavage. Here, we synthesise and fully characterise an air‐stable and hydrocarbon‐soluble uranyl phenanthroline complex, [UVIO2(NO3)2(Ph2phen)], UPh2phen, and demonstrate that it can catalytically abstract hydrogen atoms from a variety of organic substrates under visible light irradiation. We show that the commercially available parent complex, uranyl nitrate ([UVIO2(NO3)2(OH2)2]⋅4H2O; UNO3), is also competent, but from electronic spectroscopy we attribute the higher rates and selectivity of UPh2phen to ligand‐mediated electronic effects. Ketones are selectively formed over other oxygenated products (alcohols, etc.), and the catalytic oxidation of substrates containing a benzylic C−H position is particularly improved for UPh2phen. We also show uranyl‐mediated photocatalytic C−C bond cleavage in a model lignin compound for the first time.

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Guest Professor in Osaka

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).PC070193-e1544691770810.jpg

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Highlight on E-waste recycling

New advances in the E-waste recycling world:

https://www.chinadialogue.net/article/show/single/en/10829-The-treasure-hidden-in-our-gadgets

 

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