Visible light-induced palladium-carbon bond weakening in catalytically relevant T-shaped complexes.
Visible light-induced palladium-carbon bond weakening in catalytically relevant T-shaped complexes.
复制标题
可见光诱导的催化相关t形配合物中钯碳键减弱。
DOI：
10.1039/d3sc02588h
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发表时间：
2023-12-13
期刊：
影响因子：
8.4
通讯作者：
Carrow, Brad P.
中科院分区：
文献类型：
--
作者：
Waddell, Peter M.;Tian, Lei;Scavuzzo, Anthony R.;Venigalla, Lalu;Scholes, Gregory D.;Carrow, Brad P.
在钯催化过程中触发单电子氧化还原过程具有解锁新的反应机制和合成方法的潜力，这些反应机制和合成方法以前在主导钯催化的典型双电子反应歧管中不可用。我们报告说，T形有机钯（II）配合物协调的一个庞大的单膦，一类有机金属中间体的特点在一系列当代催化反应，经历蓝光促进键弱化导致温和和有效的均裂强Pd（II）-C（sp3）键在环境条件下。在这些系统中光触发自由基形成的起源，其缺乏明显的基于配体的发色团（即，π-系统），使用DFT计算，光辐射测量，和瞬态吸收光谱的组合进行了研究。现有的数据表明，T形有机钯（ii）配合物表现出不寻常的蓝光访问Pd到C（sp3）的转变。该过程的量子效率和激发态寿命出乎意料地上级以低位配体中心LUMO（π*）为特征的原型（α-二亚胺）Pd（ii）络合物。这些结果表明，协调不饱和的有机钯（II）化合物，催化剂在无数的催化过程中，具有未开发的潜力，在可见光激发下的单电子反应性。在钯催化过程中触发单电子氧化还原过程具有解锁新的反应机制和合成方法的潜力，这些反应机制和合成方法以前在主导钯催化的典型双电子反应歧管中不可用。
Triggering one-electron redox processes during palladium catalysis holds the potential to unlock new reaction mechanisms and synthetic methods not previously accessible in the typical two-electron reaction manifolds that dominate palladium catalysis. We report that T-shaped organopalladium(ii) complexes coordinated by a bulky monophosphine, a class of organometallic intermediate featured in a range of contemporary catalytic reactions, undergo blue light-promoted bond weakening leading to mild and efficient homolytic cleavage of strong Pd(ii)–C(sp3) bonds under ambient conditions. The origin of light-triggered radical formation in these systems, which lack an obvious ligand-based chromophore (i.e., π-systems), was investigated using a combination of DFT calculations, photoactinometry, and transient absorption spectroscopy. The available data suggest T-shaped organopalladium(ii) complexes manifest unusual blue light-accessible Pd-to-C(sp3) transition. The quantum efficiency and excited state lifetime of this process were unexpectedly superior compared to a prototypical (α-diimine)Pd(ii) complex featuring a low-lying, ligand-centered LUMO (π*). These results suggest coordinatively-unsaturated organopalladium(ii) compounds, catalysts in myriad catalytic processes, have untapped potential for one-electron reactivity under visible light excitation. Triggering one-electron redox processes during palladium catalysis holds the potential to unlock new reaction mechanisms and synthetic methods not previously accessible in the typical two-electron reaction manifolds that dominate palladium catalysis.
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影响因子：
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