title: Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes.
abstract: Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing ancillary ligands to promote elimination offers a strategy to circumvent the inherently short-lived excited states of 3d metal complexes for the activation of thermodynamically challenging bonds.
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Seung Jun
authors.initials: SJ
authors.lastname: Hwang
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: David C
authors.initials: DC
authors.lastname: Powers
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Maher
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Bryce L
authors.initials: BL
authors.lastname: Anderson
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Ryan G
authors.initials: RG
authors.lastname: Hadt
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Shao-Liang
authors.initials: SL
authors.lastname: Zheng
authors.affiliation: ‡ChemMatCARS, The University of Chicago, Argonne, Illinois 60439, United States.
authors.forename: Yu-Sheng
authors.initials: YS
authors.lastname: Chen
authors.affiliation: †Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D055668:Photochemical Processes; D013816:Thermodynamics
chemical_list: D002712:Chlorides; D009942:Organometallic Compounds; D009532:Nickel