Chlorine Photoelimination from a Diplatinum Core: Circumventing the Back Reaction

The d(9)center dot center dot center dot d(9) Pt-2(I,I)(tfepma)(2)Cl-2 (1) compound (tfepma = ((CF3CH2O)(2)P)(2)NCH3), d(7)-d(9) Pt-2(I,III)(tfepma)(2)Cl-4 (2) and d(7)-d(7) Pt-2(III,III)(tfepma)(2)Cl-6 (3), homologous suite of compounds have been prepared. Irradiation of 3 with visible light generates 2 in solution in the presence of 2,3-dimethyl-1,3-butadiene with a quantum efficiency of similar to 38%. The evolution of Cl-2 upon solid-state phototysis of 3 represents the first example of the thermodynamically unfavorable halogen elimination without the use of a chemical trap.