Central transcriptional regulator controls photosynthetic growth and carbon storage in response to high light.

Carbon capture and biochemical storage are some of the primary drivers of photosynthetic yield and productivity. To elucidate the mechanisms governing carbon allocation, we designed a photosynthetic light response test system for genetic and metabolic carbon assimilation tracking, using microalgae as simplified plant models. The systems biology mapping of high light-responsive photophysiology and carbon utilization dynamics between two variants of the same Picochlorum celeri species, TG1 and TG2 elucidated metabolic bottlenecks and transport rates of intermediates using instationary 13C-fluxomics. Simultaneous global gene expression dynamics showed 73% of the annotated genes responding within one hour, elucidating a singular, diel-responsive transcription factor, closely related to the CCA1/LHY clock genes in plants, with significantly altered expression in TG2. Transgenic P. celeri TG1 cells expressing the TG2 CCA1/LHY gene, showed 15% increase in growth rates and 25% increase in storage carbohydrate content, supporting a coordinating regulatory function for a single transcription factor.

Stabilizing Highly Active Ru Sites by Suppressing Lattice Oxygen Participation in Acidic Water Oxidation.

In hydrogen production, the anodic oxygen evolution reaction (OER) limits the energy conversion efficiency and also impacts stability in proton-exchange membrane water electrolyzers. Widely used Ir-based catalysts suffer from insufficient activity, while more active Ru-based catalysts tend to dissolve under OER conditions. This has been associated with the participation of lattice oxygen (lattice oxygen oxidation mechanism (LOM)), which may lead to the collapse of the crystal structure and accelerate the leaching of active Ru species, leading to low operating stability. Here we develop Sr-Ru-Ir ternary oxide electrocatalysts that achieve high OER activity and stability in acidic electrolyte. The catalysts achieve an overpotential of 190 mV at 10 mA cm-2 and the overpotential remains below 225 mV following 1,500 h of operation. X-ray absorption spectroscopy and 18O isotope-labeled online mass spectroscopy studies reveal that the participation of lattice oxygen during OER was suppressed by interactions in the Ru-O-Ir local structure, offering a picture of how stability was improved. The electronic structure of active Ru sites was modulated by Sr and Ir, optimizing the binding energetics of OER oxo-intermediates.

Artificial Intelligence Clinical Evidence Engine for Automatic Identification, Prioritization, and Extraction of Relevant Clinical Oncology Research.

PURPOSE: We developed a system to automate analysis of the clinical oncology scientific literature from bibliographic databases and match articles to specific patient cohorts to answer specific questions regarding the efficacy of a treatment. The approach attempts to replicate a clinician's mental processes when reviewing published literature in the context of a patient case. We describe the system and evaluate its performance. METHODS: We developed separate ground truth data sets for each of the tasks described in the paper. The first ground truth was used to measure the natural language processing (NLP) accuracy from approximately 1,300 papers covering approximately 3,100 statements and approximately 25 concepts; performance was evaluated using a standard F1 score. The ground truth for the expert classifier model was generated by dividing papers cited in clinical guidelines into a training set and a test set in an 80:20 ratio, and performance was evaluated for accuracy, sensitivity, and specificity. RESULTS: The NLP models were able to identify individual attributes with a 0.7-0.9 F1 score, depending on the attribute of interest. The expert classifier machine learning model was able to classify the individual records with a 0.93 accuracy (95% CI, 0.9 to 0.96, P < .0001), and sensitivity and specificity of 0.95 and 0.91, respectively. Using a decision boundary of 0.5 for the positive (expert) label, the classifier demonstrated an F1 score of 0.92. CONCLUSION: The system identified and extracted evidence from the oncology literature with a high degree of accuracy, sensitivity, and specificity. This tool enables timely access to the most relevant biomedical literature, providing critical support to evidence-based practice in areas of rapidly evolving science.

High-temperature 2D ferromagnetism in conjugated microporous porphyrin-type polymers.

The need for magnetic 2D materials that are stable to the enviroment and have high Curie temperatures is very important for various electronic and spintronic applications. We have found that two-dimensional porphyrin-type aza-conjugated microporous polymer crystals are such a material (Fe-aza-CMPs). Fe-aza-CMPs are stable to CO, CO2, and O2 atmospheres and show unusual adsorption, electronic, and magnetic properties. Indeed, they are semiconductors with small energy band gaps ranging from 0.27 eV to 0.626 eV. CO, CO2, and O2 molecules can be attached in three different ways where single, double, or triple molecules are bound to iron atoms in Fe-aza-CMPs. For different attachment configurations we find that for CO and CO2 a uniform distribution of the molecules is most energetically favorable while for O2 molecules aggregation is most energetically preferable. The magnetic moments decrease from 4 to 2 to 0 for singly, doubly, triply occupied configurations for all gasses respectively. The most interesting magnetic properties are found for O2 molecules attached to the Fe-aza-CMP. For a single attachment configuration we find that an antiferromagnetic state is favorable. When two O2 molecules are attached, the calculations show the highest exchange integral with a value of J = 1071 µeV. This value has been verified by two independent methods where in the first method J is calculated by the energy difference between ferromagnetic and anitferromagnetic configurations. The second method is based on the frozen magnon approach where the magnon dispersion curve has been fitted by the Ising model. For the second method J has been estimated at J = 1100 µeV in excellent agreement with the first method.

Reply to the 'Comment on "The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface"' by A. J. Colussi and S. Enami, Chem. Sci., 2019, 10, DOI: 10.1039/c9sc00991d.

The air-water interface serves as a crucial site for numerous chemical and physical processes in environmental science and engineering, such as cloud chemistry, ocean-atmosphere exchange, and wastewater treatment. The development of "surface-selective" techniques for probing interfacial properties of water therefore lies at the forefront of research in chemical science. Recently, researchers have adapted electrospray ionization mass spectrometry (ESIMS) to generate microdroplets of water to investigate interfacial phenomena at thermodynamic equilibrium. In contrast, using a broad set of experimental and theoretical techniques, we found that electrosprays of water could facilitate partially hydrated (gas-phase) ions (e.g., H3O+·(H2O)2) to drive/catalyze chemical reactions that are otherwise not possible to accomplish by purely interfacial effects (e.g., enhanced water-hydrophobe surface area) (Chem. Sci., 2019, 10, 2566). Thus, techniques exploiting electrosprays of water cannot be relied upon as generalized surface-selective platforms. Here, we respond to the comments raised by Colussi & Enami (Chem. Sci., 2019, 10, DOI: ; 10.1039/c9sc00991d) on our paper.

Ferromagnetism in 2D organic iron hemoglobin crystals based on nitrogenated conjugated micropore materials.

In this work we study a low-cost two-dimensional ferromagnetic semiconductor with possible applications in biomedicine, solar cells, spintronics, and energy and hydrogen storage. From first principle calculations we describe the unique electronic, transport, optical, and magnetic properties of a π-conjugated micropore polymer (CMP) with three iron atoms placed in the middle of an isolated pore locally resembling heme complexes. This material exhibits strong Fe-localized dz2 bands. The bandgap is direct and equal to 0.28 eV. The valence band is doubly degenerate at the Γ-point and for larger k-wavevectors the HOMO band becomes flat with low contribution to charge mobility. The absorption coefficient is roughly isotropic. The conductivity is also isotropic with the nonzero contribution in the energy range 0.3-8 eV. The xy-component of the imaginary part of the dielectric tensor determines the magneto-optical Faraday and Kerr rotation. Nonvanishing rotation is observed in the interval of 0.5-5.0 eV. This material is found to be a ferromagnet of an Ising type with long-range exchange interactions with a very high magnetic moment per unit cell, m = 6 µB. The exchange integral is calculated by two independent methods: (a) from the energy difference between ferromagnetic and antiferromagnetic states and (b) from a magnon dispersion curve. In the former case Jnn = 27 µeV. In the latter case the magnon dispersion is fitted by the Ising model with the nearest and next-nearest neighbor spin interactions. From these estimations we find that Jnn = 19.5 µeV and Jnnn = -3 µeV. Despite the different nature of the calculations, the exchange integrals are only within 28% difference.

The chemical reactions in electrosprays of water do not always correspond to those at the pristine air-water interface.

The recent application of electrosprays to characterize the air-water interface, along with the reports on dramatically accelerated chemical reactions in aqueous electrosprays, have sparked a broad interest. Herein, we report on complementary laboratory and in silico experiments tracking the oligomerization of isoprene, an important biogenic gas, in electrosprays and isoprene-water emulsions to differentiate the contributions of interfacial effects from those of high voltages leading to charge-separation and concentration of reactants in the electrosprays. To this end, we employed electrospray ionization mass spectrometry, proton nuclear magnetic resonance, ab initio calculations and molecular dynamics simulations. We found that the oligomerization of isoprene in aqueous electrosprays involved minimally hydrated and highly reactive hydronium ions. Those conditions, however, are non-existent at pristine air-water interfaces and oil-water emulsions under normal temperature and pressure. Thus, electrosprays should be complemented with surface-specific platforms and theoretical methods to reliably investigate chemistries at the pristine air-water interface.

Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn3MO4 Cubane and Fe3MO(OH) and Mn3MO(OH) Clusters.

The modulation of the reactivity of metal oxo species by redox inactive metals has attracted much interest due to the observation of redox inactive metal effects on processes involving electron transfer both in nature (the oxygen-evolving complex of Photosystem II) and in heterogeneous catalysis (mixed-metal oxides). Studies of small-molecule models of these systems have revealed numerous instances of effects of redox inactive metals on electron- and group-transfer reactivity. However, the heterometallic species directly involved in these transformations have rarely been structurally characterized and are often generated in situ. We have previously reported the preparation and structural characterization of multiple series of heterometallic clusters based on Mn3 and Fe3 cores and described the effects of Lewis acidity of the heterometal incorporated in these complexes on cluster reduction potential. To determine the effects of Lewis acidity of redox inactive metals on group transfer reactivity in structurally well-defined complexes, we studied [Mn3MO4], [Mn3MO(OH)], and [Fe3MO(OH)] clusters in oxygen atom transfer (OAT) reactions with phosphine substrates. The qualitative rate of OAT correlates with the Lewis acidity of the redox inactive metal, confirming that Lewis acidic metal centers can affect the chemical reactivity of metal oxo species by modulating cluster electronics.

Room temperature d0 ferromagnetism in PbS films: nonuniform distribution of Pb vacancies.

Because of the importance of ferromagnetism at room temperature, we search for new materials that can exhibit a non-vanishing magnetic moment at room temperature and at the same time can be used in spintronics. The experimental results indicate that d0 ferromagnetism without any magnetic impurities takes place in PbS films made of close-packed lead sulfide nanoparticles of 30 nm. To explain the existence of the d0 ferromagnetism, we propose a model where various PbS bulk and surface configurations of Pb-vacancies are analyzed. The bulk configurations have a zero magnetic moment while the two surface configurations with Pb vacancies with the same non-vanishing magnetic moments and lowest ground state energies contribute to the total magnetization. Based on the experimental value of the saturation magnetization, 0.2 emu g-1, we have found that the calculated Pb vacancy concentration should be about 3.5%, which is close to typical experimental values. Besides being very important for applications, there is one feature of PbS d0 ferromagnetism that makes this material special for fundamental research: PbS ferromagnetism can exhibit topologically driven spatial magnetic moment distributions (e.g., magnetic skyrmions) due to large spin-orbit coupling.

Reaction Mechanism for the Hydrogen Evolution Reaction on the Basal Plane Sulfur Vacancy Site of MoS2 Using Grand Canonical Potential Kinetics.

We develop the grand canonical potential kinetics (GCP-K) formulation based on thermodynamics from quantum mechanics calculations to provide a fundamental basis for understanding heterogeneous electrochemical reactions. Our GCP-K formulation arises naturally from minimizing the free energy using a Legendre transform relating the net charge of the system and the applied voltage. Performing this macroscopic transformation explicitly allows us to make the connection of GCP-K to the traditional Butler-Volmer kinetics. Using this GCP-K based free energy, we show how to predict both the potential and pH dependent chemistry for a specific example, the hydrogen evolution reaction (HER) at a sulfur vacancy on the basal plane of MoS2. We find that the rate-determining steps in both acidic and basic conditions are the Volmer reaction in which the second hydrogen atom is adsorbed from the solution. Using the GCP-K formulation, we show that the stretched bond distances change continuously as a function of the applied potential. This shows that the main reason for the higher activity in basic conditions is that the transition state is closer to the product, which leads to a more favorable Tafel slope of 60 mV/dec. In contrast if the transition state were closer to the reactant, where the transfer coefficient is less than 0.5 we would obtain a Tafel slope of almost 150 mV/dec. Based on this detailed understanding of the reaction mechanism, we conclude that the second hydrogen at the chalcogenide vacant site is the most active toward the hydrogen evolution reaction. Using this as a descriptor, we compare it to the other 2H group VI metal dichalcogenides and predict that vacancies on MoTe2 will have the best performance toward HER.

Catalytic Synthesis of Superlinear Alkenyl Arenes Using a Rh(I) Catalyst Supported by a "Capping Arene" Ligand: Access to Aerobic Catalysis.

Alkyl and alkenyl arenes are used in a wide range of products. However, the synthesis of 1-phenylalkanes or their alkenyl variants from arenes and alkenes is not accessible with current commercial acid-based catalytic processes. Here, it is reported that an air-stable Rh(I) complex, (5-FP)Rh(TFA)(η2-C2H4) (5-FP = 1,2-bis( N-7-azaindolyl)benzene; TFA = trifluoroacetate), serves as a catalyst precursor for the oxidative conversion of arenes and alkenes to alkenyl arenes that are precursors to 1-phenylalkanes upon hydrogenation. It has been demonstrated that coordination of the 5-FP ligand enhances catalyst longevity compared to unligated Rh(I) catalyst precursors, and the 5-FP-ligated catalyst permits in situ recycling of the Cu(II) oxidant using air. The 5-FP ligand provides a Rh catalyst that can maintain activity for arene alkenylation over at least 2 weeks in reactions at 150 °C that involve multiple Cu(II) regeneration steps using air. Conditions to achieve >13 000 catalytic turnovers with an 8:1 linear:branched (L:B) ratio have been demonstrated. In addition, the catalyst is active under aerobic conditions using air as the sole oxidant. At 80 °C, an 18:1 L:B ratio of alkenyl arenes has been observed, but the reaction rate is substantially reduced compared to 150 °C. Quantum mechanics (QM) calculations compare two predicted reaction pathways with the experimental data, showing that an oxidative addition/reductive elimination pathway is energetically favored over a pathway that involves C-H activation by concerted metalation-deprotonation. In addition, our QM computations are consistent with the observed selectivity (11:1) for linear alkenyl arene products.

Reaction Mechanism and Kinetics for Ammonia Synthesis on the Fe(111) Surface.

The Haber-Bosch industrial process for synthesis of ammonia (NH3) from hydrogen and nitrogen produces the millions of tons of ammonia gas annually needed to produce nitrates for fertilizers required to feed the earth's growing populations. This process has been optimized extensively, but it still uses enormous amounts of energy (2% of the world's supply), making it essential to dramatically improve its efficiency. To provide guidelines to accelerate this improvement, we used quantum mechanics to predict reaction mechanisms and kinetics for NH3 synthesis on Fe(111)-the best Fe single crystal surface for NH3 synthesis. We predicted the free energies of all reaction barriers for all steps in the mechanism and built these results into a kinetic Monte Carlo model for predicting steady state catalytic rates to compare with single-crystal experiments at 673 K and 20 atm. We find excellent agreement with a predicted turnover frequency (TOF) of 17.7 s-1 per 2 × 2 site (5.3 × 10-9 mol/cm2/sec) compared to TOF = 10 s-1 per site from experiment.

The Neurobiological Mechanism of Chemical Aversion (Emetic) Therapy for Alcohol Use Disorder: An fMRI Study.

A recent NIH epidemiology study found the lifetime prevalence of alcohol use disorder in the United States to be 29%. Alcohol drinking behavior is strongly "learned" via pleasure center activation/reinforcement. Alcohol craving is a powerful desire to drink alcoholic beverages. Craving was added as one of the defining criteria for alcohol use disorder in DSM5, and craving reduction is becoming an increasingly important treatment goal. In the current study, patients with alcohol use disorder received 10 days of inpatient multi-modal treatments at Schick Shadel Hospital (SSH) of Seattle. The treatments included five chemical aversion conditioning sessions that associated alcohol cues (and alcohol) with nausea and emesis. All patients met DSM4 criteria for alcohol use disorder, were heavy drinkers, and reported craving alcohol pre-treatment. Craving reduction was one of the primary treatment goals. This is the first fMRI study to measure the effects of chemical aversion therapy on alcohol craving-related brain activity. Patients were recruited as subjects for the University of Washington (UW) brain scan study following SSH admission but before treatment onset. Prior to treatment, patients reported craving/desire for alcohol. After treatment (after four SSH chemical aversion treatments, again after five SSH chemical treatments, 30 and 90-days post-discharge), these same patients reported avoidance/aversion to alcohol. Most of the participants (69%) reported being still sober 12 months post-treatment. Consistent with a craving reduction mechanism of how chemical aversion therapy facilitates sobriety, results of the UW fMRI brain scans showed significant pre- to post-treatment reductions in craving-related brain activity in the occipital cortex. Additional fMRI brain scan studies are needed to further explore the neurobiological mechanism of chemical aversion therapy treatment for alcohol use disorder, and other substance use disorders for which chemical aversion therapy is used (e.g., opioid dependence and cocaine dependence). Substance use disorders are estimated to affect well over one billion people worldwide.

The mechanism for catalytic hydrosilylation by bis(imino)pyridine iron olefin complexes supported by broken symmetry density functional theory.

Density functional theory (DFT, B3LYP-D3 with implicit solvation in toluene) was used to investigate the mechanisms of olefin hydrosilylation catalyzed by PDI(Fe) (bis(imino)pyridine iron) complexes, where PDI = 2,6-(ArN[double bond, length as m-dash]CMe)2(C5H3N) with Ar = 2,6-R2-C6H3. We find that the rate-determining step for hydrosilylation is hydride migration from Et3SiH onto the Fe-bound olefin to form (PDI)Fe(alkyl)(SiEt3). This differs from the mechanism for the Pt Karstedt catalyst in that there is no prior Si-H oxidative addition onto the Fe center. (PDI)Fe(alkyl)(SiEt3) then undergoes C-Si reductive elimination to form (PDI)Fe, which coordinates an olefin ligand to regenerate the resting state (PDI)Fe(olefin). In agreement with experimental observations, we found that anti-Markovnikov hydride migration has a 5.1 kcal mol-1 lower activation enthalpy than Markovnikov migration. This system has an unusual anti-ferromagnetic coupling between high spin electrons on the Fe center and the unpaired spin in the pi system of the non-innocent redox-active PDI ligand. To describe this with DFT, we used the "broken-symmetry" approach to establish the ground electronic and spin state of intermediates and transition states over the proposed catalytic cycles.

The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO(2) (110) Surface.

How to efficiently oxidize H2O to O2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OER at the IrO2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. This allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam.

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

The Reaction Mechanism with Free Energy Barriers for Electrochemical Dihydrogen Evolution on MoS2.

We report density functional theory (M06L) calculations including Poisson-Boltzmann solvation to determine the reaction pathways and barriers for the hydrogen evolution reaction (HER) on MoS2, using both a periodic two-dimensional slab and a Mo10S21 cluster model. We find that the HER mechanism involves protonation of the electron rich molybdenum hydride site (Volmer-Heyrovsky mechanism), leading to a calculated free energy barrier of 17.9 kcal/mol, in good agreement with the barrier of 19.9 kcal/mol estimated from the experimental turnover frequency. Hydronium protonation of the hydride on the Mo site is 21.3 kcal/mol more favorable than protonation of the hydrogen on the S site because the electrons localized on the Mo-H bond are readily transferred to form dihydrogen with hydronium. We predict the Volmer-Tafel mechanism in which hydrogen atoms bound to molybdenum and sulfur sites recombine to form H2 has a barrier of 22.6 kcal/mol. Starting with hydrogen atoms on adjacent sulfur atoms, the Volmer-Tafel mechanism goes instead through the M-H + S-H pathway. In discussions of metal chalcogenide HER catalysis, the S-H bond energy has been proposed as the critical parameter. However, we find that the sulfur-hydrogen species is not an important intermediate since the free energy of this species does not play a direct role in determining the effective activation barrier. Rather we suggest that the kinetic barrier should be used as a descriptor for reactivity, rather than the equilibrium thermodynamics. This is supported by the agreement between the calculated barrier and the experimental turnover frequency. These results suggest that to design a more reactive catalyst from edge exposed MoS2, one should focus on lowering the reaction barrier between the metal hydride and a proton from the hydronium in solution.

Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization.

A series of rhodium(III) bis(quinolinyl)benzene (bisq(x)) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisq(x)) ligand candidates involving different functional groups to determine the impact on Rh(III)(bisq(x))-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is Rh(III) coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η(2)-benzene coordination mode of (bisq(x)) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.

A Model of In vitro Plasticity at the Parallel Fiber-Molecular Layer Interneuron Synapses.

Theoretical and computational models of the cerebellum typically focus on the role of parallel fiber (PF)-Purkinje cell (PKJ) synapses for learned behavior, but few emphasize the role of the molecular layer interneurons (MLIs)-the stellate and basket cells. A number of recent experimental results suggest the role of MLIs is more important than previous models put forth. We investigate learning at PF-MLI synapses and propose a mathematical model to describe plasticity at this synapse. We perform computer simulations with this form of learning using a spiking neuron model of the MLI and show that it reproduces six in vitro experimental results in addition to simulating four novel protocols. Further, we show how this plasticity model can predict the results of other experimental protocols that are not simulated. Finally, we hypothesize what the biological mechanisms are for changes in synaptic efficacy that embody the phenomenological model proposed here.

Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H(+).

The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2P(E)Py(E)P(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H(+) to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H(+) versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.