title: High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes.
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.
authors.affiliation: University of Missouri, Columbia, Missouri 65211, USA.
authors.forename: Alice Raphael
authors.initials: AR
authors.lastname: Karikachery
authors.forename: Han Baek
authors.initials: HB
authors.lastname: Lee
authors.forename: Mehdi
authors.initials: M
authors.lastname: Masjedi
authors.forename: Andreas
authors.initials: A
authors.lastname: Ross
authors.forename: Morgan A
authors.initials: MA
authors.lastname: Moody
authors.forename: Xiaochen
authors.initials: X
authors.lastname: Cai
authors.forename: Megan
authors.initials: M
authors.lastname: Chui
authors.forename: Carl D
authors.initials: CD
authors.lastname: Hoff
authors.forename: Paul R
authors.initials: PR
authors.lastname: Sharp