Hydroboration Reduction of CO2 Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO2 Self-Promoting Single Active-Site Mechanisms and Counterion Effects,ACS Catalysis

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Hydroboration Reduction of CO2 Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO2 Self-Promoting Single Active-Site Mechanisms and Counterion Effects
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-12-19 , DOI: 10.1021/acscatal.3c04386
Lin Zhang ₁ , Ming Lei ₂ , Zexing Cao ₁

Affiliation

Hydroboration reduction of CO₂ by HBpin catalyzed by ambiphilic boron centers, a doubly reduced 9,10-dimethyl-9,10-dihydro-9,10-diboraanthracene [DBA-Me₂]^2– (A0) and its metal salts (^MA0) reported by Wagner, M. ( Angew. Chem., Int. Ed. 2018, 57, 16491–16495), has been explored by density functional theory (DFT) calculations. Unexpectedly, the cycloadduct (A1^a) from the barrier-free activation of CO₂ and bridging across the two B atoms of A0 may serve as a highly active catalyst to boost the CO₂ hydroboration reduction through a single active-site mechanism. The catalytic hydroboration of CO₂ by dianion A0 and its metal salts M_n-[DBA-Me₂] (n = 2 for M = Li⁺, Na⁺, K⁺; and n = 1 for M = Mg²⁺, Ca²⁺) follows the double active-site mechanism, where the diboron site acts as the active center. Generally, the CO₂ hydroboration reduction by HBpin may take place through three independent and cascade subcycles, leading to primary HCOOBpin, secondary HCHO, and reduction product CH₃OBpin, respectively. Counter cations and THF solvent molecules remarkably influence the activation of HBpin and H₂ by A0, but the relative energetics of the overall hydroboration process mediated by A1^a is less changed. The present results show that the doubly reduced arylborane and its CO₂ adduct, as well as their metal salts are quite promising for the hydroboration reduction of CO₂.

中文翻译：

双还原芳基硼烷催化 CO2 硼氢化还原：DFT 洞察双活性位点和 CO2 自促进单活性位点机制和抗衡离子效应

两亲性硼中心、双重还原的 9,10-二甲基-9,10-二氢-9,10-二硼蒽 [DBA-Me ₂ ] ^2– ( A0 ) 及其金属盐 ( ^M ) 催化 HBpin 硼氢化还原 CO ₂A0 ) 报告者瓦格纳，M.( Angew. Chem., Int. Ed. 2018 , 57 , 16491–16495) 已通过密度泛函理论 (DFT) 计算进行了探索。_{出乎意料的是，CO 2}的无障碍活化和桥接A0的两个B原子形成的环加合物( A1a ⁾可以作为高活性催化剂，通过单一活性位点机制促进CO _{2 硼氢化还原。}二阴离子A0_及其金属盐Mn _- [DBA-Me ₂ ] ( n = 2 for M = Li ⁺ , Na ⁺ , K ⁺ ; and n = 1 for M = Mg 2+ , Ca n = 1 for M = Mg ²⁺ , Ca ²⁺ )遵循双活性位点机制，其中二硼位点充当活性中心。一般而言，HBpin的CO ₂硼氢化还原可通过三个独立且级联的子循环进行，分别产生初级HCOOBpin、次级HCHO和还原产物CH ₃ OBpin。抗衡阳离子和THF溶剂分子显着影响A0对HBpin和H ₂的活化，但由A1a介导的整个硼氢化过程的相对能量^变化较小。目前的结果表明，双还原芳基硼烷及其CO ₂加合物以及它们的金属盐在CO ₂的硼氢化还原方面非常有前景。

更新日期：2023-12-19

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