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Ligand-Dominated Activation of CO 2 and CS 2 by the Putative Nickel Phosphiniminato Intermediates.
Inorganic Chemistry 2024 April 18
Room-temperature photoactivation of the first- and second-generation PN3 P-pincer nickel azido complexes 1a and 1b in the presence of CO2 or CS2 afforded N-bound carbamates, dithiocarbamates, and isothiocyanates, providing insights into CO2 and CS2 activation and demonstrating how a seemingly small difference in the ligand structure significantly influences the reactivity. Theoretical calculations disclosed that the charge of the phosphorus atom plays a critical role in determining the nitrogen atom transfer to form a plausible nickel phosphiniminato intermediate.
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