Photocrystallographic observation of halide-bridged intermediates in halogen photoeliminations.

ABSTRACT: Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal-metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal-metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterizatio

SUBMITTER: Powers DC 

PROVIDER: S-EPMC4227815 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature