High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes
Inorganic Chemistry2013Vol. 52(7), pp. 4113–4119
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Alice Raphael Karikachery, Han Baek Lee, Mehdi Masjedi, Andreas Ross, Morgan A. Moody, Xiaochen Cai, Megan Chui, Carl D. Hoff, Paul R. Sharp
Abstract
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 Br2. 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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