Nh4pf6

All materials were used as received. The ligands [9]aneS 3 , btp, pbt, as well as NH 4 PF 6 were purchased from Sigma-Aldrich. The ligand [9]aneS 2 O was prepared as previously reported. 14 Palladium(II) acetate was purchased from Strem. The ligands fpp, bzq, and ppyCHO were purchased from TCI. Cyclometallated acetate dimers used in the preparation of 1b, 3b, 4b, and 5b were prepared as previously reported. 8 [Pd( ppy) Cl] 2 was prepared by the reported method. 47 All synthetic manipulations were carried out in air. Elemental analyses were performed by Atlantic Microlab. Fourier transform IR spectra were obtained for solid samples using a PerkinElmer Spectrum One FTIR with diamond ATR accessory. Proton and carbon-13 NMR spectra were obtained on a JEOL 400 MHz NMR spectrometer using residual solvent for both the deuterium lock and reference. Variable temperature measurements were performed using a JEOL temperature-controlled probe. Samples were held at each temperature for 10 min prior to acquisition of each spectrum. After spectra were collected at the lowest and highest temperatures recorded, room temperature spectra were recollected and compared with the initial room temperature spectra to ensure equilibrium NMR measurements were acquired. Mass spectra were acquired using a Thermo LCQ Fleet ESI-MS.