On the Synergy of Coulombic and Chelate Effects in Bidentate Diboranes: Synthesis and Anion Binding Properties of a Cationic 1,8-Diborylnaphthalene

As part of our investigation in the chemistry of bidentate Lewis acids for anion complexation, we have carried out the reaction of 1-(dimesitylboryl)-8-(1′-bora-9′-thia-anthryl)­naphthalene (<b>1</b>) with methyltriflate. This reaction proceeds via alkylation of the sulfur atom to afford a bidentate diborane ([<b>2</b>]⁺) decorated by a peripheral sulfonium unit. This new diborane, which has been isolated as the triflate salt, reacts with both fluoride and azide anions to form the corresponding anion chelate complexes <b>2</b>-μ₂-F and <b>2</b>-μ₂-N₃, respectively. Titration experiments carried out in chloroform indicate that the fluoride binding constant of [<b>2</b>]⁺ exceeds that of <b>1</b> by at least 4 orders of magnitude. These results, which are supported by spectroscopic, structural, and computational data, show that chelate and Coulombic effects are additive and can be combined to boost the anion affinity of bidentate Lewis acids

Insight Understanding of Ultrathin Carbon-Deficient Molybdenum Carbide Catalytic Activity for CO₂ Conversion into Hydrocarbon Fuels

The catalytic reduction of carbon dioxide (CO2) to produce methane (CH4) as a hydrocarbon fuel has attracted extensive attention for renewable energy. In this study, we investigate ultrathin carbon-deficient molybdenum carbide (MoC0.66) as a catalyst for CO2 capture and conversion. Our findings indicate that MoC0.66 possesses remarkable catalytic activity for CO2 hydrogenation to CH4. Interestingly, unlike conventional catalysts, the limiting step of the MoC0.66 catalyst is determined by the release of *OH species during the CO2 reduction reaction (CO2RR). Increasing the temperature can improve the release of H2O and CH4 as well as the selectivity of the CO2RR. Moreover, the increase of temperature promotes the CO2RR on MoC0.66 by increasing the reaction rate, as evidenced by both simulation and experimental results. These results provide a way for the understanding of insight mechanisms for the CO2RR to energy-rich fuels at the atomic level and guide experimental applications of carbon-neutral reactions

On the Synergy of Coulombic and Chelate Effects in Bidentate Diboranes: Synthesis and Anion Binding Properties of a Cationic 1,8-Diborylnaphthalene

As part of our investigation in the chemistry of bidentate Lewis acids for anion complexation, we have carried out the reaction of 1-(dimesitylboryl)-8-(1′-bora-9′-thia-anthryl)­naphthalene (<b>1</b>) with methyltriflate. This reaction proceeds via alkylation of the sulfur atom to afford a bidentate diborane ([<b>2</b>]⁺) decorated by a peripheral sulfonium unit. This new diborane, which has been isolated as the triflate salt, reacts with both fluoride and azide anions to form the corresponding anion chelate complexes <b>2</b>-μ₂-F and <b>2</b>-μ₂-N₃, respectively. Titration experiments carried out in chloroform indicate that the fluoride binding constant of [<b>2</b>]⁺ exceeds that of <b>1</b> by at least 4 orders of magnitude. These results, which are supported by spectroscopic, structural, and computational data, show that chelate and Coulombic effects are additive and can be combined to boost the anion affinity of bidentate Lewis acids

Topographies of the corresponding ERP effects.

<p>A: Topography of the semantic relatedness effects (time-locked to the Noun). B: Topography of the semantic relatedness effects (time-locked to the Verb) at different levels of thematic relation. C: Topography of the thematic relation effects (time-locked to the Verb) at different levels of semantic relatedness.</p

The word frequency and number of strokes of the Nouns.

<p>B: The word frequency, number of strokes, and neighborhood size of the Verbs. High-agent indicates ‘high-relatedness, agent’ condition; High-patient indicates ‘high-relatedness, patient’ condition; Low-agent indicates ‘low-relatedness, agent’ condition; Low-patient indicates ‘low-relatedness, patient’ condition.</p

Example stimuli of all the four conditions used in the current study.

<p>Note: High-agent indicates ‘high-relatedness, agent’ condition; High-patient indicates ‘high-relatedness, patient’ condition; Low-agent indicates ‘low-relatedness, agent’ condition; Low-patient indicates ‘low-relatedness, patient’ condition. The underlined words are the critical words (Verb).</p

Grand-average ERPs time-locked to the Nouns in the low-relatedness and the high-relatedness conditions.

<p>Grand-average ERPs time-locked to the Nouns in the low-relatedness and the high-relatedness conditions.</p

Time-frequency analysis of electroencephalogram series in the four experimental conditions.

<p>A: Event-related spectral perturbation (ERSP) from electrode P3. Black square frames indicate the time window and frequency for which there are significant differences between the agent and patient conditions; dotted black square frames indicate the time window and frequency for which there are significant differences between the high_relatedness and low_relatedness conditions. B: Topographies of the thematic relation effect of beta power (15–30 Hz) and the semantic relatedness effect of theta power (4–7 Hz).</p

Grand-average ERPs time-locked to the Verbs in the four experimental conditions.

<p>Grand-average ERPs time-locked to the Verbs in the four experimental conditions.</p

The results of the behavioral experiment.

<p>A: Accuracy rate for the question sentences in the four experimental conditions; B: The reading time at the disambiguating Verb; C: The reading time at the word ‘le’ immediately following the Verb. High-agent indicates ‘high-relatedness, agent’ condition; High-patient indicates ‘high-relatedness, patient’ condition; Low-agent indicates ‘low-relatedness, agent’ condition; Low-patient indicates ‘low-relatedness, patient’ condition.</p