Hsueh, Fang-CheBarluzzi, LucianoKeener, MeganRajeshkumar, ThayalanMaron, LaurentScopelliti, RosarioMazzanti, Marinella2022-03-102022-03-102022-03-102022-02-0910.1021/jacs.1c13150https://infoscience.epfl.ch/handle/20.500.14299/186117Thorium nitrides are likely intermediates in the reported cleavage and functionalization of dinitrogen by molecular thorium complexes and are attractive compounds for the study of multiple bond formation in f-element chemistry, but only one example of thorium nitride isolable from solution was reported. Here, we show that stable multimetallic azide/nitride thorium complexes can be generated by reduction of thorium azide precursors─a route that has failed so far to produce Th nitrides. Once isolated, the thorium azide/nitride clusters, M3Th═N═Th (M = K or Cs), are stable in solutions probably due to the presence of alkali ions capping the nitride, but their synthesis requires a careful control of the reaction conditions (solvent, temperature, nature of precursor, and alkali ion). The nature of the cation plays an important role in generating a nitride product and results in large structural differences with a bent Th═N═Th moiety found in the K-bound nitride as a result of a strong K–nitride interaction and a linear arrangement in the Cs-bound nitride. Reactivity studies demonstrated the ability of Th nitrides to cleave CO in ambient conditions yielding CN–.text::journal::journal article::research article