Polyoxometalates arise as significant catalysts in the field of organic chemistry due to their diverse properties and functions. Recent progress based on experimental evidence and density functional theory (DFT) calculations provides valuable information to demystify the chemistry of decatungstate anion, W₁₀O₃₂⁴⁻. Particularly, functionalization of aldehydes by homolytic C–H bond cleavage can be efficiently achieved when it is catalyzed by this polyoxometalate. Two reaction mechanisms have been formulated to account for the role of W₁₀O₃₂⁴⁻ in organic chemical reactions: the single electron transfer and the hydrogen atom transfer (HAT) mechanisms. In this contribution, the HAT pathway for the acylation of dimethyl maleate is experimentally and quantum-chemically explored in detail. Results based on DFT calculations under the unrestricted formalism suggest that the acylation occurs in a barrierless process upon the formation of the lowest-in-energy triplet excited state of W₁₀O₃₂⁴⁻. These outcomes agree well with the experimental evidence since the acylated adduct was produced at a 90% yield; in this regard, side reactions like radical couplings and decarbonylation resulted in less competitiveness. The current work may therefore help in the comprehension of the mechanistic details leading to the synthesis of organic compounds photocatalyzed by polyoxometalates, even under solar radiation.

中文翻译：

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分解钨酸根阴离子对马来酸二甲酯的酰化作用：对氢原子转移反应机理的认识

多金属氧酸盐由于其多种性质和功能而成为有机化学领域的重要催化剂。基于实验证据和密度泛函理论（DFT）计算的最新进展提供了有价值的信息，可以使去离子重金属阴离子W ₁₀ O ₃₂ ⁴⁻的化学脱神秘。特别是，当醛被该多金属氧酸盐催化时，可以通过均一的C–H键断裂来有效地实现醛的官能化。制定了两种反应机理来解释W ₁₀ O ₃₂ ^{4−的作用}在有机化学反应中：单电子转移和氢原子转移（HAT）机理。在这一贡献中，对马来酸二甲酯的酰化作用的HAT途径进行了实验和量子化学的详细研究。根据无限制形式主义下的DFT计算得出的结果表明，在W ₁₀ O ₃₂ ⁴⁻的能量最低的三重态激发态形成后，酰化反应会在无障碍过程中发生。。这些结果与实验证据非常吻合，因为酰化的加合物的收率为90％。在这方面，诸如自由基偶联和脱羰基的副反应导致竞争力降低。因此，当前的工作可能有助于理解机械细节，即使在太阳辐射下，也可以合成由多金属氧酸盐光催化的有机化合物。