Low Oxidation State Cobalt Center Stabilized by a Covalent Organic Framework to Promote Hydroboration of Olefins,ACS Catalysis

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Low Oxidation State Cobalt Center Stabilized by a Covalent Organic Framework to Promote Hydroboration of Olefins
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-02-15 , DOI: 10.1021/acscatal.2c05442
Luis Gutiérrez _{1,

2} , Vlad Martin-Diaconescu ₃ , Carla Casadevall ₄ , Freddy Oropeza ₅ , Victor A. de la Peña O’Shea ₅ , JingJing Meng ₁ , Manuel A. Ortuño ₆ , Julio Lloret-Fillol _{1,

7}

Affiliation

Site isolation of unstable catalytic species within a reticular material is an appealing strategy for mitigating catalyst decomposition while creating catalysts with improved activity and robustness. The covalent organic framework (COF) based on single cobalt sites coordinated to 2,2′-bipyridine (COF_bpyCo) exploits the isolated nature of the cobalt sites to stabilize low-valent single sites and catalyze the hydroboration of olefins. Terminal alkyl boronate esters were obtained using 1 mol % COF_bpyCo loading starting from terminal alkenes and internal alkenes, thanks to a tandem isomerization-hydroboration process. The catalytic activity of COF_bpyCo was maintained after being recycled six times. Experimental and computational studies suggested the {(bpy^•–)Co^I(THF)₂} moiety as the active catalytic species within the COF. The mechanism follows an oxidative boryl migration, followed by isomerization and reductive elimination to form the boronate ester.

中文翻译：

低氧化态钴中心由共价有机骨架稳定以促进烯烃的硼氢化

网状材料内不稳定催化物质的位点隔离是一种有吸引力的策略，可减轻催化剂分解，同时产生具有更高活性和稳健性的催化剂。基于与 2,2'-联吡啶 ( COF _bpy Co ) 配位的单个钴位点的共价有机框架 (COF) 利用钴位点的孤立性质来稳定低价单位点并催化烯烃的硼氢化反应。通过串联异构化-硼氢化过程，从末端烯烃和内部烯烃开始，使用 1 mol% COF _bpy Co负载获得末端烷基硼酸酯。COF _bpy Co的催化活性被回收六次后得到维护。实验和计算研究表明 {(bpy ^•– )Co ^I (THF) ₂ } 部分是 COF 中的活性催化物质。该机制遵循氧化硼基迁移，然后异构化和还原消除以形成硼酸酯。

更新日期：2023-02-15

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