Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.
The cationic pyridine adduct of a ruthenium complex bearing a chelating benzylidene and an N-heterocyclic carbene was identified as an intermediate during the activation of cis dichloro species and a novel triggering concept for olefin metathesis catalysts based on cationic species was disclosed.
The synthesis and characterization of two new ruthenium indenylidene complexes [RuCl(2)(SIPr)(Py)(Ind)] 6 and [RuCl(2)(SIPr)(3-BrPy)(Ind)] 7 featuring the sterically demanding N-heterocyclic carbene 1,3-bis(2,6-di isopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr) are reported. Remarkable activity was observed with these complexes in ring closing, enyne, and cross metathesis of olefins at low catalyst loadings. The performance of SIPr-bearing complexes 6 and 7 as well as [RuCl(2)(SIPr)(PCy(3))(Ind)] 5 in ring opening metathesis polymerization is also disclosed. This work highlights the enormous influence of the neutral "spectator" ligands on catalyst activity and stability.
The aim of the present study is to develop readily available and stable pre-catalysts that could be easily prepared on large scale from simple starting materials. Based on the hypothesis that substitution of classical PCy(3) with phosphanes of varying electron-donating properties could be a straightforward manner to improve catalytic activity, a methodical study dealing with the effect of phosphane fine-tuning in ruthenium-indenylidene catalysts was performed. Challenged to establish how the electronic properties of para-substituted phosphane ligands translate into catalyst activity, the versatile behaviour of these new ruthenium-indenylidene complexes was investigated for a number of metathesis reactions.
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