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Stepwise B–H bond activation of a meta-carborane
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2021-08-10 , DOI: 10.1039/d1qi00732g
Xin-Ran Liu 1 , Peng-Fei Cui 1 , Shu-Ting Guo 1 , Run-Ze Yuan 1 , Guo-Xin Jin 1, 2
Affiliation  

Stepwise multiple B–H bond activation is a major challenge in synthetic chemistry. Herein, we have developed a controlled stepwise method to monitor the process of B–H bond activation based on a meta-carborane. In this process, the metallacyclic 3 [Pd2(C10N2H8)2(SCNPh)4(m-C2B10H10)2] can be achieved through non-covalent bond interactions between the carboranylthioamide ligand and transition metal fragment. Importantly, it slowly converts to product 4 [Pd(C10N2H8)(SCNPh)(SCNHPh)(m-C2B10H9)] via mono B–H bond activation, and then a second B–H activation leads to 5 [Pd2(C10N2H8)2(SCNPh)2(m-C2B10H8)]. The obtained organometallic palladium pincer complex shows acid–base responsive behaviour, namely reversible structural transformation between the mononuclear pincer complex and a trimetallic Pd/S metallacycle. This work provides a potential strategy for exploring the mechanisms of B–H bond activation.

中文翻译:

间碳硼烷的逐步 B-H 键活化

逐步多重 B-H 键活化是合成化学中的一个主要挑战。在此,我们开发了一种受控的逐步方法来监测基于碳硼烷的 B-H 键活化过程。在这个过程中,金属环3 [Pd 2 (C 10 N 2 H 8 ) 2 (SCNPh) 4 ( m -C 2 B 10 H 10 ) 2 ] 可以通过碳硼烷硫代酰胺配体和过渡之间的非共价键相互作用来实现金属碎片。重要的是,它缓慢地转化为产物4 [Pd(C 10N 2 H 8 )(SCNPh)(SCNHPh)( m -C 2 B 10 H 9 )]通过单 B–H 键活化,然后第二次 B–H 活化导致5 [Pd 2 (C 10 N 2 H 8 ) 2 (SCNPh) 2 ( m -C 2 B 10 H 8)]。获得的有机金属钯钳形配合物显示出酸碱响应行为,即单核钳形配合物和三金属 Pd/S 金属环之间的可逆结构转变。这项工作为探索 B-H 键激活机制提供了一种潜在的策略。
更新日期:2021-08-16
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