Photoinduced Ligand-to-Metal Charge Transfer of Cobaltocene: Radical Release and Catalytic Cyclotrimerization
Photoinduced Ligand-to-Metal Charge Transfer of Cobaltocene: Radical Release and Catalytic Cyclotrimerization
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DOI：
10.1021/acs.inorgchem.2c03779
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发表时间：
2023-01-26
影响因子：
4.6
通讯作者：
V. Prather，Keaton
中科院分区：
文献类型：
--
作者：
Tsui，Emily Y.;V. Prather，Keaton
在配体到金属的电荷转移能上辐照钴金属茂烯导致环戊二烯-钴键的不稳定和自由基的释放。环戊二烯基自由基是通过电子顺磁共振（EPR）光谱检测的，使用自旋阱，也可以用氢原子供体试剂进行化学捕获。该反应提供了一种新的光化学方法来生成新的钴配合物或形成对催化[2 + 2 + 2]环三聚化反应有活性的环戊二烯基钴(I)。更重要的是，这些结果还表明，在许多条件下，包括与光伏或光催化有关的条件下，钴二烯不应被视为光稳定的氧化还原试剂。
Irradiation of cobalt metallocenes at the ligand-to-metal charge transfer energies results in the labilization of the cyclopentadienyl–cobalt bond and radical release. The cyclopentadienyl radical is detected by electron paramagnetic resonance (EPR) spectroscopy using a spin trap and can also be chemically trapped using hydrogen-atom-donating reagents. This reaction presents a new photochemical method of generating new cobalt complexes or of forming cyclopentadienyl cobalt(I) species that are active for catalytic [2 + 2 + 2] cyclotrimerization reactions. More importantly, these results also show that cobaltocene should not be considered as a photostable redox reagent under many conditions, including those relevant to photovoltaics or photocatalysis.