Conformational Change with Steric Interactions Affects the Inner Sphere Component of Concerted Proton-Electron Transfer in a Pyridyl-Appended Radical Cation System.

Proton-coupled electron transfer (PCET) model systems combine one-electron oxidants and bases to generate net hydrogen atom acceptors. We have generated two persistent pyridyl-appended radical cations: 10-(pyrid-2-yl)-10H-phenothiazinium (PPT•+) and 3-(pyrid-2-yl)-10-methyl-10H-phenothiazinium (MPTP•+). EPR spectra and corresponding calculations indicate phenothiazinium radical cations with minimal spin on the pyridine nitrogen.

Synthesis and characterization of aluminum-α-diimine complexes over multiple redox states.

The aluminum complexes (LMes(2-))AlCl(THF) (3) and (LDipp(-))AlCl2 (4) (LMes = N,N'-bis[2,4,6-trimethylphenyl]-2,3-dimethyl-1,4-diazabutadiene, LDipp = N,N'-bis[2,6-diisopropylphenyl]-2,3-dimethyl-1,4-diazabutadiene) were prepared by direct reduction of the ligands with sodium metal followed by salt metathesis with AlCl3. The (LMes(-))AlCl2 (5) complex was prepared through one-electron oxidative functionalization of 3 with either AgCl or CuCl. Complex 3 was characterized using (1)H and (13)C NMR spectoscopies.