Hydrogen Bond-Assisted PCET and Formation of W^III─OH in Bis(Dithiolene) Complex.

ABSTRACT: The redox non-innocent nature of dithiolene ligands is well known for stabilizing high-valent metal ions and facilitating proton-coupled electron transfer (PCET) processes. Until now, proton reactivity at the dithiolene site has been primarily associated with low-valent metal centers, as high-valent metal-dithiolene complexes were not considered viable for such reactivity. This study introduces high-valent bis(dithiolene) tungsten (W)-oxo complexes featuring hydrogen-bonding interactions, unveiling a novel proton reduction mechanism mediated by the dithiolene moiety. The process begins with a nucleophilic W-oxo, forming a hydrogen bond, followed by a second hydrogen bond at the dithiolene-sulfur (S) site. These hydrogen-bonding interactions significantly modulate the molecular orbital ener

SUBMITTER: Lee W 

PROVIDER: S-EPMC12304848 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature