New methoxy substituted CNC pincers form ruthenium catalysts that are robust and convert CO2 to CO selectively using light energy.

The photocatalytic reduction of CO2 can generate a number of products with CO and HCO2 – being two of the most commonly observed. Frequently, the selective formation of one of these products is presumed to be the result of catalyst design. However, several common variables are present when exploring the photocatalytic CO2 reduction reaction. In order to better understand the origin of selectivity in this reaction, the choices of solvent, electron and proton source, photosensitizer (PS), and catalyst were evaluated in photocatalytic CO2 reduction reactions. Intriguingly, highly selective catalysts for CO or HCO2 – under one set of conditions can be transformed by these environmental choices into becoming highly selective for the opposite product while retaining high turnover numbers. This highlights the importance of carefully considering reaction conditions before ascribing catalyst selectivity to an inherent molecular design property.

Five ruthenium catalysts described herein facilitate self-sensitized carbon dioxide reduction to form carbon monoxide with a ruthenium catalytic center. These catalysts include four new and one previously reported CNC pincer complexes featuring a pyridinol derived N-donor and N-heterocyclic carbene (NHC) C-donors derived from imidazole or benzimidazole. The complexes have been characterized fully by spectroscopic and analytic methods, including X-ray crystallography. Introduction of a 2,2′-bipyridine (bipy) coligand and phenyl groups on the NHC ligand was necessary for rapid catalysis. [(CNC)­Ru­(bipy)­(CH3CN)]­(OTf)2 is among the most active and durable photocatalysts in the literature for CO2 reduction without an external photosensitizer. The role of the structure of this complex in catalysis is discussed, including the importance of the pincer’s phenyl wingtips, the bipyridyl ligand, and a weakly coordinating monodentate ligand.

Ten ruthenium pincer complexes were evaluated as catalysts for the hydrodeoxygenation (HDO) reaction on a lignin monomer surrogate, vanillyl alcohol. Four of these complexes are reported herein with the synthesis and full characterization data for all and single-crystal X-ray diffraction data for three complexes bearing OH/O − , NMe 2 , and Me substituents on the pincer. A systematic study of these CNC pincer complexes revealed that the π-donor substituent on the pyridine ring plays a key role in enhancing the yield of the desired deoxygenated product. While OMe, OH, and NMe 2 are all effective as π-donor substituents on the central pyridine ring in the pincer, the highest conversion to products and the best selectivity was observed with OH substituents and added sodium carbonate as a base. Base serves to deprotonate the OH group and form 1 Oas observed spectroscopically. Furthermore, efforts to use other catalysts have revealed that free or labile sites are needed on the ruthenium center and an electronically rich and nonbulky CNC pincer is optimal. At low catalyst loadings (0.01 mol %), the OH-substituted catalyst 1 OH in the presence of base serves as a homogeneous catalyst and is able to achieve quantitative and selective conversion of vanillyl alcohol to desired the HDO product, creosol, with up to 10000 turnovers. With this knowledge in hand, we can design the next generation of homogeneous catalysts with increased reactivity toward all of the oxygenated sites on lignin-derived monomers.

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.

The reactivity of three ruthenium electrocatalysts is shown to be modulated through the addition of anions for more selective and faster electrocatalysis. Controlled potential electrolysis studies confirm the generation of CO from CO 2. The Faradaic efficiency increased for the three ruthenium catalysts studied through the introduction of Clto the reaction solution. Interestingly, a neutral ruthenium coordination complex with an associated chloride also gave equal or faster rates of catalysis upon Cl À addition. In this report, a systematic study on the effects of added halides (I À , Br À , Cl À , and F À) with varied counter cations (K + and TBA +) with and without water is examined. Computational analysis provides insights into this interesting increase in FE based on anion addition. These results show anion addition to electrocatalysis reaction mixtures add an additional parameter to increase both rate and selectivity of catalysis with one example improving from 19 % FE to 91 % FE for CO production.

Seven ruthenium catalysts with the general formula [(CNC)Ru(CH 3 CN) 2 Cl]OTf have been used to understand structure function relationships in the sensitized photocatalytic CO 2 reduction reaction. Herein, CNC is a pincer ligand containing imidazole-based N-heterocyclic carbenes (NHCs) attached to a central pyridyl ring with R groups at the 3-or 4-position. Two new complexes (R = 3-OMe, 4-NPh 2) have been fully characterized by analytical and spectroscopic methods and single-crystal X-ray diffraction. Furthermore, three previously synthesized complexes (R = 4-Me, 4-NMe 2 , and 4-OH) are used for photoca-[a

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