High Quantum
Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV)
Complexes
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Abstract
Pt(IV)
complexes <i>trans</i>-Pt(PEt<sub>3</sub>)<sub>2</sub>(R)(Br)<sub>3</sub> (R = Br, aryl and polycyclic aromatic fragments) photoeliminate
molecular bromine with quantum yields as high as 82%. Photoelimination
occurs both in the solid state and in solution. Calorimetry measurements
and DFT calculations (PMe<sub>3</sub> analogs) indicate endothermic
and endergonic photoeliminations with free energies from 2 to 22 kcal/mol
of Br<sub>2</sub>. Solution trapping experiments with high concentrations
of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor
to bromine elimination
