Carbon monoxide (CO) is an attractive C1 building block for the construction of more complex organic molecules. In the past few years there has been increased interest in reactions that combine two (or more) molecules of CO to construct carbon chains. Controlling selectivity in these reactions is important; both the chain length and the ratio of C:H:O are key factors. Focusing on C2 products, it has been shown that two equivalents of CO can be combined at reducing metal centres to form ethynediolates, ethenediolates, ethanediolates, ketenes, an acetaldehyde enolate, and ethene. Isocyanides (CNR, R = alkyl, aryl) are isoelectronic with CO. Related reactions that combine two or more equivalents of isocyanide to form homo-coupled products are widely reported (Figure ). When considering these studies, an obvious question arises as to whether it might be possible to combine CO and CNR to form cross-coupled products. For the C2 series this would potentially lead to the formation of products containing a 1,2-difunctionalised carbon chain with vicinal oxygen and nitrogen containing functional groups. Such substitution patterns are found in aminoacids, -2 Precedent for the cross-coupling of CO with CNR is limited to a handful of examples. Stepwise reaction of CO and CNR with a zirconium(IV) dialkyl complex to form a substituted ethene amidolate was reported as early as 1985. This type of reactivity has been observed at group 4 metal dialkyl complexes supported by alkoxide, tropocoronand, and N-heterocyclic carbene ligands. Related titanocyclobutane complexes, and seven coordinate niobium and tantalum complexes have also been reported to react with CO and CNR to form substituted ethene amidolates. In contrast, a thorium alkyl complex was shown to react with CO and CNR to form a ketenimine species. Binuclear silylene compounds are known to cross-couple and deoxygenated CO and CNR to form functionalised ketenimine products. To the best of our knowledge, despite nearly 40 In this paper, we report the stepwise cross-coupling of CO and CNXyl (Xyl = 2,6-dimethylphenyl) using a tetrametallic magnesium hydride complex. This reaction results in the generation of the simplest known ethene amidolate ligand. We suggest that the reaction is under kinetic control, and that the metal cluster is essential to template reactivity, as simpler dimeric magnesium hydride complexes do not lead to ethene amidolate formation. DFT calculations are used to probe the electronic structure of the coordinated ethene amidolate fragment and rationalise the most likely mechanism of its formation. Finally, we show that the ethene amidolate ligand is labile and can be transferred to alternative metals and semi-metals (e.g. Al, B) providing access to a unique 1,2-difunctionalised C2 ligand derived from CO.