Multielectron Bond Cleavage Processes Enabled by Redox-Responsive Phosphinimide Ligands.

ABSTRACT: The activation of small molecules via multielectron redox processes offers promise in mediating difficult transformations related to energy conversion processes. While molecular systems that engage in one- and two-electron redox processes are widespread, those that participate in the direct transfer of four or more electrons to small molecules are very rare. To that end, we report a mononuclear Cr^II complex competent for the 4-electron reduction of dioxygen (O₂) and nitrosoarenes. These systems additionally engage in facile two-electron group transfer reactivity, including O atom excision and nitrene transfer. Structural, spectroscopic, and computational studies support bond activation processes that intimately occur at a mononuclear chromium(phosphinimide) center and highlight the unusual structural responsiveness of the phosphinimides in stabilizing a range of metal redox states.

SUBMITTER: Winslow CC 

PROVIDER: S-EPMC10618924 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature