Halogen Photoreductive Elimination from Gold(III) Centers
datasetposted on 2009-06-03, 00:00 authored by Thomas S. Teets, Daniel G. Nocera
Monomeric complexes of the type AuIII(PR3)X3 and bimetallic complexes of the type Au2I,III[μ-CH2(R2P)2]X4 and Au2III,III[μ-CH2(R2P)2]X6 (R = Ph, Cy, X = Cl−, Br−) undergo facile photoelimination of halogen. M−X bond activation and halogen elimination is achieved upon LMCT excitation of solutions of AuIII complexes in the presence of olefin chemical traps. As opposed to the typical one-electron redox transformations of LMCT photochemistry, the LMCT photochemistry of the AuIII centers allows for the unprecedented (i) two-electron photoelimination of X2 from a monomeric center and (ii) four-electron photoelimination of X2 from a bimetalllic center. The quantum yields for X2 photoproduction, in general, are between 10% and 20% for all species, showing only minimal dependence on the identity of the ligands about gold, or the nuclearity of the complex. Efficient X2 photoelimination is observed in the absence of a chemical trap, providing a rare example of authentic, trap-free halogen elimination from a transition metal center.