Reversible homolytic activation of water via metal-ligand cooperativity in a T-shaped Ni(ii) complex.

ABSTRACT: A T-shaped Ni(ii) complex [^Tol,PhDHPy]Ni has been prepared and characterized. EPR spectra and DFT calculations of this complex suggest that the electronic structure is best described as a high-spin Ni(ii) center antiferromagnetically coupled with a ligand-based radical. This complex reacts with water at room temperature to generate the dimeric complex [^Tol,PhDHPy]Ni(μ-OH)Ni[^Tol,PhDHPyH] which has been thoroughly characterized by SXRD, NMR, IR and deuterium-labeling experiments. Addition of simple ligands such as phosphines or pyridine displaces water and demonstrates the reversibility of water activation in this system. The water activation step has been examined by kinetic studies and DFT calculations which suggest an unusual homolytic reaction via

SUBMITTER: Chang MC 

PROVIDER: S-EPMC6354739 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature