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MXenes are a new family of 2D carbides or nitrides that have attracted attention due to their layered structure, tunable surface groups and high electrical conductivity. Here, we report for the first time that Ti 2 CT x MXene catalyses the selective oxidative dehydrogenation of n -butane to butenes and 1,3-butadiene. This catalyst showed higher intrinsic activity compared to commercial TiC and TiO 2 samples in terms of C 4 olefin formation rate. We propose that the stabilisation of structural vacancies and the change in composition (from a carbide to a mixed phase oxide) in the MXene causes its higher catalytic activity. These vacancies can lead to a higher concentration of unpaired electrons in the MXene-derived material, enhancing its nucleophilic properties and favouring the production of olefins. We thank the Netherlands Organization for Scientific Research (NWO) for the grant “Developing novel catalytic materials for converting CO2, methane and ethane to high-value chemicals in a hybrid plasma-catalytic reactor” (China.15.119). EVRF thanks the “Ministerio de Ciencia e innovación” grant (PID2020-116998RB-I00).

Reaction of the Rh(II) dimer [LRh]2(μ-Br)2 (L = ([2,6-Me2C6H3NCMe]2CH) with the bulky amide LiNH(2,6-iPr2C6H3) leads to a monomeric Rh(II) amide with a T-shape N3Rh arrangement and a pronounced agostic interaction. Reaction with the less bulky LiNH(2,6-Me2C6H3) results in benzylic C-H activation to a binuclear complex with a unique aza-xylylene bridging mode. With LiNHC6H5 we observe initial formation of [LRh]2(μ-NHPh)2 followed by N,C2′ coupling of two anilines. These reactions can be explained based on aminyl radical character of the Rh(II) amides (supported by EPR evidence) and/or involvement of nitrene intermediates.