Durable
catalysts based on abundant metals are needed for the photocatalytic
CO2 reduction reaction (PCO2RR). Thus, we synthesized
a series of low-valent cobalt(I) complexes, [(CNC)Co(CO)2]+[Co(CO)4]−, with H (1Co‑
) or OMe (2Co‑
) in the 4-position of the pyridyl N donor group (where CNC
= L1 and L2 from double deprotonation of
the [CNC]2+ preligands L1(HOTf)2
= 1,1′-(pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium) ditriflate and L2(HOTf)2
= 1,1′-(4-methoxypyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium) ditriflate). Anion exchange for [BArF24]− (tetrakis(3,5-trifluoromethyl)phenyl)borate)
produced 1 and 2 and phosphine substitution
produced 1PMe3
, 1PPh3
, and 2PPh3
complexes with the structure
[(CNC)Co(CO)(PR′3)]+[BArF24]−. In 1DPPP
, the DPPP
ligand bridges two Co(I) centers (DPPP = 1,3-bis(diphenylphosphino)propane).
All complexes were fully characterized, and electrochemical measurements
suggest that for most of the phosphine complexes, CO2 binding
by the complex occurs prior to reduction due to a vacant coordination
site. Intriguingly, the introduction of a phosphine ligand resulted
in a geometry change from trigonal bipyramidal to square pyramidal
which correlates to preassociation of CO2 to the complex
and higher reactivity in the PCO2RR. Complexes 1, 1PMe3
, 1PPh3
, 1DPPP
, 2, 2PPh3
, and Na[Co(CO)4] are PCO2RR catalysts with
a methoxy substituent deactivating and a phosphine ligand activating.
With monodentate phosphines, catalyst 1PPh3
(1 μM) had the highest turnover frequency (TOFM = 3.9 h–1) and turnover number (TON = 199). The
dinuclear 1DPPP
complex was the most active
and robust catalyst with TON = 278 and TOF = 21.1 h–1 at 1 μM loading. Under dilute conditions (1 nM), 1PPh3
produced up to 36,000 TON with TOF = ∼800
h–1 over 6 days, which shows that this is a durable
molecular catalyst acting with fast rates in the PCO2RR.
Thus, stabilizing low-valent cobalt can offer a unique entry point
to highly active PCO2RR catalysts. While cobalt(I) has
been proposed as a catalytic species, catalysts that start from Co(I)
have not been made previously and the use of phosphine co-ligands
has allowed these catalysts to achieve high activity.