Electronic design criteria for O-O bond formation via metal-oxo complexes.
Metal-oxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metal-oxo is central to the formation of O-O bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of O-O bonds at metal-oxo active sites are presented. The acid-base (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metal-oxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metal-oxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metal-oxos of an odd d electron count are needed to drive O-O coupling. This Forum Article focuses on the different electronic structures of terminal metal-oxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures.
Betley
Theodore A
TA
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
Wu
Qin
Q
Van Voorhis
Troy
T
Nocera
Daniel G
DG
D001665:Binding Sites; D006878:Hydroxides / Q000737:chemistry; D007700:Kinetics; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D014867:Water / Q000737:chemistry
D006878:Hydroxides; D008670:Metals; D014867:Water; D010100:Oxygen