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

Martin Ertl; Uwe Monkowius; Kerstin T Oppelt

doi:10.1021/acs.inorgchem.3c02925

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

Inorg Chem. 2023 Oct 23;62(42):17510-17521. doi: 10.1021/acs.inorgchem.3c02925. Epub 2023 Oct 6.

Authors

Martin Ertl¹, Uwe Monkowius¹, Kerstin T Oppelt²

Affiliations

¹ Linz School of Education─Chemistry, Johannes Kepler University Linz, Altenberger Strasse 69, 4040 Linz, Austria.
² Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland.

Abstract

This study reports on Re tricarbonyl complexes bearing 8-(diphenylphosphanyl)quinoline, P∩N, and 8-(diphenylarsanyl)quinoline, As∩N, as bidendate ligands. We studied the reactivity of these complexes in comparison with fac-Re(N∩N)(CO)₃Cl (with N∩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∩N)Cl and Re(CO)₃(As∩N)Cl complexes also in the presence of protons.