Ligand-Dominated Activation of CO2 and CS2 by the Putative Nickel Phosphiniminato Intermediates

Room-temperature photoactivation of the first- and second-generation PN3P-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 d...

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Published inInorganic chemistry Vol. 63; no. 17; pp. 7820 - 7827
Main Authors Yao, Changguang, Gonçalves, Théo P., Wang, Xiufang, Luo, Lun, Huang, Kuo-Wei
Format Journal Article
LanguageEnglish
Published American Chemical Society 29.04.2024
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Summary:Room-temperature photoactivation of the first- and second-generation PN3P-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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ISSN:0020-1669
1520-510X
1520-510X
DOI:10.1021/acs.inorgchem.4c00429