Ligand-field transition-induced C–S bond formation from nickelacycles
Jeongcheol Shin, Jiseon Lee, Jong‐Min Suh, Kiyoung Park
Abstract
times enhancement for the C-S bond-forming reductive elimination reaction upon Ni-centered ligand-field transitions. The effects of excitation energy and ancillary ligands on photoactivity have been investigated with 17 different nickelacycle species in combination with four corresponding acyclic complexes. Spectroscopic and computational electronic structural characterizations reveal that, regardless of coordinated species, d-d transitions can induce Ni-C bond homolysis, and that the reactivity of the resulting Ni(i) species determines the products of the overall reaction. The photoactivity mechanism established in this study provides general insights into the excited-state chemistry of organonickel(ii) complexes.