Reduction
of CO<sub>2</sub> to Methanol Catalyzed
by a Biomimetic Organo-Hydride Produced from Pyridine
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Abstract
We use quantum chemical calculations
to elucidate a viable mechanism
for pyridine-catalyzed reduction of CO<sub>2</sub> to methanol involving
homogeneous catalytic steps. The first phase of the catalytic cycle
involves generation of the key catalytic agent, 1,2-dihydropyridine
(<b>PyH</b><sub><b>2</b></sub>). First, pyridine (Py)
undergoes a H<sup>+</sup> transfer (PT) to form pyridinium (PyH<sup>+</sup>), followed by an e<sup>–</sup> transfer (ET) to produce
pyridinium radical (PyH<sup>0</sup>). Examples of systems to effect
this ET to populate PyH<sup>+</sup>’s LUMO (<i>E</i><sup>0</sup><sub>calc</sub> ∼ −1.3 V vs SCE) to form
the solution phase PyH<sup>0</sup> via highly reducing electrons include
the photoelectrochemical p-GaP system (<i>E</i><sub>CBM</sub> ∼ −1.5 V vs SCE at pH 5) and the photochemical [Ru(phen)<sub>3</sub>]<sup>2+</sup>/ascorbate system. We predict that PyH<sup>0</sup> undergoes further PT–ET steps to form the key closed-shell,
dearomatized (<b>PyH</b><sub><b>2</b></sub>) species (with
the PT capable of being assisted by a negatively biased cathode).
Our proposed sequential PT–ET–PT–ET mechanism
for transforming Py into <b>PyH</b><sub><b>2</b></sub> is analogous to that described in the formation of related dihydropyridines.
Because it is driven by its proclivity to regain aromaticity, <b>PyH</b><sub><b>2</b></sub> is a potent recyclable organo-hydride
donor that mimics important aspects of the role of NADPH in the formation
of C–H bonds in the photosynthetic CO<sub>2</sub> reduction
process. In particular, in the second phase of the catalytic cycle,
which involves three separate reduction steps, we predict that the <b>PyH</b><sub><b>2</b></sub>/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 CO<sub>2</sub> and its two succeeding intermediates, namely,
formic acid and formaldehyde, to ultimately form CH<sub>3</sub>OH.
The hydride and proton transfers for the first of these reduction
steps, the homogeneous reduction of CO<sub>2</sub>, 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