Journal
INORGANIC CHEMISTRY
Volume 52, Issue 7, Pages 4113-4119Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic4004998
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Funding
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-FG02-88ER13880]
- National Science Foundation [CHE 0615743]
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Pt(IV) complexes trans-Pt(PEt3)(2)(R)(Br)(3) (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 (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br-2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.
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