D 2 O, DMSO-d 6 , and CDCl 3 were purchased from Cambridge Isotope Laboratory Inc; tetra p-sulfonatophenyl porphyrin from Tokyo Chemical Industry (TCI); (Rh(CO) 2 Cl) 2 from Strem Chemicals Inc; and all other chemicals were purchased from Aldrich or Alfa Aesar unless otherwise noted and used as received. 1 H NMR spectra were recorded on a Bruker AVII + -400 spectrometer at ambient temperature and the chemical shifts were referenced to 3-trimethylsilyl-1 propanesulfonic acid sodium salt. GC-MS

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... sults were obtained by the Agilent 7890A/5975C GC/MSD system equipped with the DB-17MS(30m, 0.25mm, 0.25um) column. Preparation of Na 3 [(TSPP)Rh III (D 2 O) 2 ] (1): Synthesis and the equilibrium distribution of [(TSPP)Rh III (D 2 O) 2 ] -3 , [(TSPP)Rh III (D 2 O)(OD)] -4 , and [(TSPP)Rh III (OD) 2 ] -5 were reported in the previously published papers. 1 H NMR (D 2 O, 400 MHz) δ(ppm): 9.15 (s, 8H, pyrrole), 8.44 (d, 8H, o-phenyl, J1 H-1 H =8Hz), 8.25 (d, 8H, m-phenyl, J1 H-1 H =8Hz). Typical procedure for preparation of (TSPP)Rh-CH 2 CH(OD)R in water: Alkenes (0.01mmol) and 1 (1.1mg, 0.001mmol) were dissolved in 0.4 mL borate buffer D 2 O solution (pH = 9.0) in vacuum adapted NMR tubes at room temperature, respectively. The progress of the reaction was monitored by 1 H NMR spectroscopy. Typical procedure for β-hydrogen elimination of (TSPP)Rh-CH 2 CH(OD)R in water: The (TSPP)Rh-CH 2 CH(OD)R complexes were prepared according to the procedure given above, which exclusively converted (TSPP)Rh III into (TSPP)Rh-CH 2 CH(OD)R. The excess of alkenes and solvent D 2 O were pumped out. Fresh D 2 O was added into the NMR tube and subjected to three freeze-pump-thaw cycles. The initial 1 H NMR was recorded to show the formation of Rh-CH 2 CH(OD)R and a clean range from 0 to 4 ppm. The sample