title: Reactions of Indene and Indoles with Platinum Methyl Cations: Indene C-H Activation, Indole πvs.Nitrogen Lone-Pair Coordination.
abstract: Reactions of indene and various substituted indoles with [(diimine)PtII(Me)(TFE)]+cations have been studied (diimine = ArN = C(Me) - C(Me) = NAr; TFE = 2,2,2-trifluoroethanol). Indene displaces the TFE ligand from platinum to form a stable π coordination complex that, upon heating, undergoes C-H activation with first order kinetics,ΔH‡= 29 kcal/mol,ΔS‡= 10 eu, and a kinetic isotope effect of 1.1 at 60 °C. Indoles also initially form coordination complexes through the C2=C3 olefin, but these undergo rearrangement to the correspondingN-bound complexes. The relative rates of initial coordination and rearrangement are affected by excess acid or methyl substitution on indole.
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (U. S. A.).
authors.forename: Travis J
authors.initials: TJ
authors.lastname: Williams
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (U. S. A.).
authors.forename: Jay A
authors.initials: JA
authors.lastname: Labinger
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, CA 91125 (U. S. A.).
authors.forename: John E
authors.initials: JE
authors.lastname: Bercaw