This study uncovers the interconnected reactivity of the three catalytically active sites of an atomically precise nanocluster Cr(py)CoSeL ((py), L = PhPNTol, Ph = phenyl, Tol = 4-tolyl). Catalytic and stoichiometric studies into tosyl azide activation and carbodiimide formation enabled the isolation and crystallographic characterization of key catalytically competent metal-imido intermediates, including the tris(imido) cluster (NTs), the catalytic resting state (NTs)(CNBu), and the site-differentiated mono(imido) cluster (NTs)(CNBu). In the stoichiometric regime, nitrene transfer proceeds via a stepwise mechanism, with the three active sites engaging sequentially to produce carbodiimide. Moreover, the chemical state of neighboring active sites was found to regulate the affinity for substrates of an individual Cr-imido edge site, as revealed by comparative structural analysis and CNBu binding studies.
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