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

被引：38

作者：

Karikachery, Alice Raphael ^{[1
]}

Lee, Han Baek ^{[1
]}

Masjedi, Mehdi ^{[1
]}

Ross, Andreas ^{[1
]}

Moody, Morgan A. ^{[1
]}

Cai, Xiaochen ^{[2
]}

Chui, Megan ^{[2
]}

Hoff, Carl D. ^{[2
]}

Sharp, Paul R. ^{[1
]}

机构：

[1] Univ Missouri, Columbia, MO 65211 USA

[2] Univ Miami, Dept Chem, Coral Gables, FL 33146 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 07期

基金：

美国国家科学基金会;

关键词：

HALOGEN PHOTOREDUCTIVE ELIMINATION; FLASH-PHOTOLYSIS; PTCL62-COMPLEX; PTBR62-COMPLEX; PHOTOCHEMISTRY; OXIDATION; SOLAR; CHEMISTRY; HYDROGEN; WATER;

D O I：

10.1021/ic4004998

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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.

引用

页码：4113 / 4119

页数：7

共 53 条

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