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 the 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 equivalents 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.