Unexpected Redox Chemistry of P∧N- and As∧N-Rhenium(I) Tricarbonyl Complexes in the Presence of CO2 Acting as an Acid

This study reports on Re tricarbonyl complexes bearing 8-(diphenylphosphanyl)quinoline, P boolean AND N, and 8-(diphenylarsanyl)quinoline, As boolean AND N, as bidendate ligands. We studied the reactivity of these complexes in comparison with fac-Re(N boolean AND N)(CO)(3)Cl (with N boolean AND N = 2,2 '-bipyridine or 4,4 '-dimethyl-2,2 '-bipyridine). We used a combination of electrochemical and spectroelectrochemical methods with time-resolved spectroscopy over 10 orders of magnitude (100 ps-1 s) to investigate the peculiar reactivity of one-electron-reduced Re(CO)(3)(P boolean AND N)Cl and Re(CO)(3)(As boolean AND N)Cl complexes also in the presence of protons.