Reagents, spectroscopy, and electrochemistry

Reagents were typically purchased from Sigma-Aldrich, Alfa Aesar, or Acros and used as received. DBU and TBAOH (as a 1.0 M solution in MeOH) were purchased from Alfa Aesar. Solvents were obtained from Fisher and deuterated solvents were obtained from Cambridge Isotope Laboratories. Deuterated solvents were dried over molecular sieves before use. n-Butyllithium (1.6 M solution in hexanes) was obtained from Acros. Methyl 2- and 4-bromobenzoate were obtained from Sigma-Aldrich. Fluorene and 2-benzoylbenzoic acid were purchased from Eastman. Methyltriphenylphosphonium bromide, potassium tert-butoxide, and rhodamine B were purchased from Acros. [CoCp2]PF6 was purchased from Strem Chemicals. All oxidants used were hexafluorophosphate (PF6) salts. Aminium (7) and ferrocenium (4) oxidants were prepared as described previously. CoCp*2 was purchased from Sigma-Aldrich and purified before use by dissolving the metallocene in a minimal amount of pentane, filtering, and concentrating the filtrate in vacuo in a N2-filled dry box.

NMR samples following MS-CPET reactions were prepared in a N2-filled glovebox using degassed solvents dried over activated 3 Å molecular sieves. NMR spectra were collected on Agilent DD2 400, DD2 500, or DD2 600 MHz spectrometers. Representative NMR spectra are found in the Supplementary Materials (figs. S3 to S5). IR spectra (fig. S6) were collected in a N2-filled glovebox on a Bruker Alpha FT-IR spectrometer in a cell using CaF2 windows.

Oxidant E1/2 values for all aminium oxidants were taken from Rhile et al. (7). E1/2 for FeCp*2+ was taken from Connelly et al. (18). Cyclic voltammograms of CoCp2 and FeCpCp* were taken in a N2-filled glovebox using a three-electrode setup in MeCN with 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6) as the supporting electrolyte. The working electrode was glassy carbon, and the auxiliary electrode was a Pt electrode. A silver wire pseudoreference was used. The silver wire was polished and placed in a capillary containing 0.1 M TBAPF6 in MeCN and separated from solution with a Vycor tip. Scans were internally referenced to ferrocene (FeCp2+/0). The concentrations of CoCp2, FeCpCp*, and FeCp2 were each ca. 1 mM. Where appropriate, literature Eo values were corrected to Fc+/0 reference using (18) or (21).

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