Metal-free binding and coupling of carbon monoxide at a boron-boron triple bond

Many metal-containing compounds, and some metal-free compounds, will bind carbon monoxide. However, only a handful of metal-containing compounds have been shown to induce the coupling of two or more CO molecules, potentially a method for use of CO as a one-carbon-atom building block for the synthesis of organic molecules. In this work, CO was added to a boron-boron triple bond at room temperature and atmospheric pressure, resulting in a compound into which four equivalent of CO are incorporated: a flat, bicyclic, bis(boralactone). By the controlled addition of one CO to the diboryne compound, an intermediate in the CO coupling reaction was isolated and structurally characterized. Electrochemical measurements confirm the strongly reducing nature of the diboryne compound

Activation of Small Molecules by U(III) Cyclooctatetraene and Pentalene Complexes

The low-valent complexes of uranium (i.e. those containing U(III) centres) are characterised as reactive, highly reducing species that can effect novel, and potentially useful, transformations of small molecules. In this chapter we review one particular class of these compounds - those supported by cyclooctatetraene and pentalene ligands - whose reduction chemistry has recently demonstrated novel and unexpected results, including the cyclooligomerisation of CO. The syntheses and structures of these compounds are presented, and their reactivity towards a variety of small molecules is examined and reviewed. The reactivity towards carbon monoxide is discussed in reference to the historical development of obtaining oxocarbons from CO

The role of uranium–arene bonding in H2O reduction catalysis

International audienceThe reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H-2 from H2O. Here, we present the precise role of uranium-arene delta bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in d bonding. The redox activity of the arene anchor and a covalent delta-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts