Reduction of CO2 to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine

We use quantum chemical calculations to elucidate a viable mechanism for pyridine-catalyzed reduction of CO2 to methanol involving homogeneous catalytic steps. The first phase of the catalytic cycle involves generation of the key catalytic agent, 1,2-dihydropyridine (PyH2). First, pyridine (Py) undergoes a H+ transfer (PT) to form pyridinium (PyH+), followed by an e transfer (ET) to produce pyridinium radical (PyH0). Examples of systems to effect this ET to populate PyH(+)s LUMO (E-calc(c)0 similar to -1.3 V vs SCE) to form the solution phase PyH0 via highly reducing electrons include the photoelectrochemical p-GaP system (E-CBM(c)0 similar to -1.5 V vs SCE at pH 5) and the photochemical [Ru(phen)(3)](2+)/ascorbate system. We predict that PyH0 undergoes further PTET steps to form the key closed-shell, dearomatized (PyH2) species (with the PT capable of being assisted by a negatively biased cathode). Our proposed sequential PTETPTET mechanism for transforming Py into PyH2 is analogous to that described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics important aspects of the role of NADPH in the formation of CH bonds in the photosynthetic CO2 reduction process. In particular, in the second phase of the catalytic cycle, which involves three separate reduction steps, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely, formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first of these reduction steps, the homogeneous reduction of CO2, are sequential in nature (in which the formate to formic acid protonation can be assisted by a negatively biased cathode). In contrast, these transfers are coupled in each of the two subsequent homogeneous hydride and proton transfer steps to reduce formic acid and formaldehyde.