High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes

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• 作者：Alice Raphael Karikachery ; Han Baek Lee ; Mehdi Masjedi ; Andreas Ross ; Morgan A. Moody ; Xiaochen Cai ; Megan Chui ; Carl D. Hoff ; Paul R. Sharp
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 1, 2013
• 年：2013
• 卷：52
• 期：7
• 页码：4113-4119
• 全文大小：347K
• 年卷期：v.52,no.7(April 1, 2013)
• ISSN：1520-510X

文摘

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.