Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, South Korea.
Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon 34141, South Korea.
J Am Chem Soc. 2020 Nov 11;142(45):19052-19057. doi: 10.1021/jacs.0c09982. Epub 2020 Oct 30.
A single molecular rhodium catalyst system (PC2-CpRh) bearing two functional domains for both photosensitization and C-H carbometalation was designed to enable an intramolecular redox process. The hypothesized charge-transfer species (PC2-CpRh) was characterized by spectroscopic and electrochemical analyses. This photoinduced internal oxidation allows a facile access to the triplet state of the key post-transmetalation intermediate that readily undergoes C-C bond-forming reductive elimination with a lower activation barrier than in its singlet state, thus enabling catalytic C-H arylation and methylation processes.
设计了一种含有两个功能结构域的单分子铑催化剂体系（PC2-CpRh），用于同时进行光致敏化和 C-H 碳金属化反应，以实现分子内氧化还原过程。通过光谱和电化学分析对假设的电荷转移物种（PC2-CpRh）进行了表征。这种光诱导的内氧化作用可以轻易地使关键的转金属后中间态进入三重态，该中间态在三重态下比单重态更容易发生 C-C 键形成的还原消除反应，从而实现了催化的 C-H 芳基化和甲基化反应。
