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Updated: Sep 22, 2025

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions
Published on: June 16, 2014
Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst
Jonathan A Kephart1, Benjamin S Mitchell1, Werner Kaminsky1
1Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Abstract:
This study uncovers the interconnected reactivity of the three catalytically active sites of an atomically precise nanocluster Cr3(py)3Co6Se8L6 (1(py)3, L = Ph2PNTol-, 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 1(NTs)3, the catalytic resting state 1(NTs)3(CNBu)3, and the site-differentiated mono(imido) cluster 1(NTs)(CNBu)2. 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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