biostudies-literaturePan HRNational Science and Technology Council27855-27861https://www.ebi.ac.uk/biostudies/studies/S-EPMC12333028biostudies-literatureUnknown147(31)The selective oxidation of strong C-H bonds remains a central challenge in synthetic chemistry, in part due to the elusive nature of active oxidants and their underlying mechanisms. Herein, we report the isolation and complete characterization of a room-temperature-stable mononuclear Ni(III)-hydroxo complex, [Na(15c5)][Ni(PS3″)(OH)] ([Na(15c5)][<b>2</b>]), supported by a <i>tris</i>(benzenethiolato)phosphine ligand derivative. The X-ray crystallographic structure of <b>2</b> reveals a trigonal bipyramidal Ni(III) center, in which the coordinated hydroxo ligand is stabilized by secondary coordination sphere interactions. Complex <b>2</b> displays hydrogen atom transfer (HAT) reactivity toward strong C-H bonds, including that in cyclohexane (BDE = 99.5 kcal mol^-1). Kinetic studiesJournal of the American Chemical SocietyBasicity-Controlled C-H Bond Activation by a Structurally Characterized Ni(III)-Hydroxo Complex.PMC12333028NSTC 1132113M006003Pan HRWu JHsu HFTsai CMLiao PJfalseBasicity-Controlled C-H Bond Activation by a Structurally Characterized Ni(III)-Hydroxo Complex.The selective oxidation of strong C-H bonds remains a central challenge in synthetic chemistry, in part due to the elusive nature of active oxidants and their underlying mechanisms. Herein, we report the isolation and complete characterization of a room-temperature-stable mononuclear Ni(III)-hydroxo complex, [Na(15c5)][Ni(PS3″)(OH)] ([Na(15c5)][<b>2</b>]), supported by a <i>tris</i>(benzenethiolato)phosphine ligand derivative. The X-ray crystallographic structure of <b>2</b> reveals a trigonal bipyramidal Ni(III) center, in which the coordinated hydroxo ligand is stabilized by secondary coordination sphere interactions. Complex <b>2</b> displays hydrogen atom transfer (HAT) reactivity toward strong C-H bonds, including that in cyclohexane (BDE = 99.5 kcal mol^-1). Kinetic studies2025-01-01T00:00:00Z2025 Aug2026-04-15T19:21:40.138Z2026-04-07T14:00:57.053ZS-EPMC123330284070985510.1021/jacs.5c06941